Fluorine-free titanocenes and the use thereof

ABSTRACT

Fluorine-free titanocene compounds of the formula I or II ##STR1## in which both R 1  radicals are preferably, independently of one another, cyclopentadienyl.sup.⊖, which is unsubstituted or substituted by alkyl,alkoxy or --Si(R 2 ) 3 , and both R 2  radicals are, in particular, alkyl, ##STR2## Z is --NR 10  --, --0-- or --S--, Y is Cl, Br, I, CN, SCN, --O--CO--CH 3 , --O--CO--phenyl or --O--SO 2  --CH 3 , 
     n is 1 or 2, 
     m is 0 or 1, where the sum of n and m must be 2, 
     R 3 , R 4  and R 5  are in particular, independently of one another, hydrogen, Cl, alkyl, cycloalkyl, adamantyl, phenyl, pyrryl or biphenylyl, where these radicals are unsubstituted or substituted by alkyl, Cl, alkylthio, --NR 8  R 9 , phenyl, phenylthio or C 1  -C 10  alkoxy, or R 3 , R 4  and R 5  are alkenyl, alkoxy, cycloalkoxy, phenoxy, benzyloxy, tetrahydrofurfuryloxy, alkylthio, cycloalkylthio, benzylthio or phenylthio, where R 3  and R 4  are not simultaneously hydrogen, and 
     if Q is a pyrimidyl radical, at least one radical R 3  or R 4  is alkoxy, cycloalkoxy, phenoxy, benzyloxy, tetrahydrofurfuryloxy or alkenyloxy, and 
     if Z is --NR 10  --, R 3  and R 4  are Cl Br or I, both radicals R 6 , independently of one another, are alkyl or alkenyl or both radicals R 6  together with the nitrogen atom to which they are bonded, form a morpholino radical, 
     R 7  is alkyl, cycloalkyl or phenyl, 
     R 8  is phenyl or α-tertiary C 4  -C 6  alkyl, 
     R 9  is, in particular, hydrogen, alkyl, cycloalkyl, phenyl or a ##STR3##  radical, where, in addition, the two R 9  radicals in --N(R 9 ) 2  are identical or different and, together with the nitrogen atom to which they are bonded, may form a 5- or 6-membered heterocyclic ring which, in addition to the nitrogen atom, may also contain further nitrogen, oxygen or sulfur atoms, 
     R 10  is as defined for R 9  or additionally, in particular, is phenyl which is unsubstituted or substituted by Cl, C 1  -C 12  alkyl, C 1  -C 10  alkoxy, C 1  -C 8  alkylthio, phenylthio, morpholino or --N(C 1  -C 4  alkyl) 2 , 
     X is --O--, --S--, ##STR4##  methylene or ethylene, and A is C 1  -C 12  alkylene or --X--A--X-- is a direct bond, are suitable as photoinitiators for photopolymerisation of compounds containing ethylenically unsaturated double bonds.

The invention relates to novel, fluorine-free titanocenes, to the usethereof as photoinitiators, and to compositions which contain thesetitanocenes.

Titanocene compounds are known as highly effective photoinitiators. U.S.Pat. Nos. 4,590,287 and 4,910,121 describe, for example, titanocenes asphotoinitiators which are substituted on the aromatic ring by halogen,alkyl or amino radicals. U.S. Pat. No. 4,548,891 discloses the use ofthese compounds as photoinitiators for the production of relief plates.U.S. Pat. Nos. 4,713,401 and 4,855,468 disclose titanocene compoundswhich are substituted on the aromatic radicals by at least onetrifiuoromethyl group. U.S. Pat. No. 4,963,470 discloses titanoceneswhich are substituted on the cyclopentadienyl ring by trialkylsiliconradicals. Titanocene compounds containing nitrogen substituents andheterocyclic substituents on the aromatic ring are disclosed in U.S.Pat. Nos. 5,008,302, 5,026,625 and 5,068,371. U.S. Pat. No. 5,192,642describes titanocenes which carry ester substituents on the aromaticradical. The titanocene compounds described in the above prior art whichare effective as photoinitiators have one thing in common: the aromaticligands on the titanium atom are substituted by fluorine ortrifiuoromethyl groups in at least one ortho-position to the carbon atombonded to the titanium. L. Summers, R. H. Uloth and A. Holmers, J. Am.Chem. Soc. 77, 3604 (1959), note thatbis(alkylaryl)bis(cyclopentadienyl)titanium compounds have only lowstability. M. A. Chaudari, P. M. Treichel and F. G. A. Stone compare thestability of titanocenes having perfluorinated aryl ligands with thecorresponding halogen-free titanocenes (J. Organomet. Chem. 2, 206-212(1964)). The titanocenes containing the perfluorinated aromatic radicalsprove to be significantly more stable. The same result is obtained inthe investigations by R. Uson, J. Fornids and M. Tomas, J. Organomet.Chem. 358, 525-543 (1988), where the fluorine substitution in theortho-position plays an important role.

The handling, preparation and disposal of fluorine-containing compoundsis frequently not simple to achieve in industry. There is therefore ademand for titanocenes which can be used as photoinitiators, but containno fluorine atoms.

It has now been found, surprisingly, that titanocene compoundscontaining pyrimidine ligands are stable, even without substitution byfluorine, and are effective photoinitiators.

The invention therefore relates to compounds of the formulae I and II##STR5## in which both R₁ radicals are, independently of one another,cyclopentadienyl.sup.⊖, indenyl.sup.⊖ or4,5,6,7-tetrahydroindenyl.sup.⊖, these radicals being unsubstituted orsubstituted by C₁ -C₁₈ alkyl, C₁ -C₁₈ alkoxy, C₂ -C₁₈ alkenyl, C₅ -C₈cycloalkyl, C₁ -C₄ alkyl-C₅ -C₈ cycloalkyl, phenyl, naphthyl,phenyl-substituted C₁ -C₁₂ alkyl, --Si(R₂)₃, --Ge(R₂)₃, cyano, Cl Br orI, and

the two R₂ radicals, independently of one another, are C₁ -C₁₂ alkyl, C₅-C₈ cycloalkyl, or unsubstituted or C₁ -C₆ alkyl-substituted phenyl orbenzyl,

Q is a ##STR6## radical, Z is --NR₁₀ --, --O-- or --S--,

Y is Cl Br, I, CN, SCN, --O--CO--CH₃, --O--CO--phenyl or --O--SO₂ --CH₃,

n is 1 or 2,

m is 0 or 1, where the sum of n and m must be 2,

R₃, R₄ and R₅, independently of one another, are hydrogen, Cl, Br, I,unsubstituted or C₁ -C₄ alkoxy-, C₅ -C₆ cycloalkyl- orphenyl-substituted C₁ -C₁₂ alkyl, unsubstituted or C₁ -C₄alkyl-substituted C₃ -C₈ cycloalkyl or adamantyl, or R₃, R₄ and R₅ arephenyl, pyrryl, furyl, thienyl, imidazolyl, pyridyl, naphthyl, anthryl,phenanthryl or biphenylyl where the radicals phenyl, pyrryl, furyl,thienyl, imidazolyl, pyridyl, naphthyl, anthryl, phenanthryl orbiphenylyl are unsubstituted or substituted by C₁ -C₁₂ alkyl,cyclopentyl, cyclohexyl, Cl, Br, I, C₁ -C₈ alkylthio, --NR₈ R₉, phenyl,phenylthio or/and C₁ -C₁₀ alkoxy, or R₃, R₄ and R₅ are unsubstituted C₂-C₁₂ alkenyl or C₂ -C₁₂ alkenyl which is substituted by unsubstituted orC₁ -C₄ alkyl-, C₁ -C₄ alkoxy-, C₁ -C₄ alkylthio-, Cl-, Br- orI-substituted phenyl or ##STR7## or R₃, R₄ and R₅ are unsubstituted orC₅ -C₈ cycloalkyl- or phenoxy-substituted C₁ -C₁₂ alkoxy, C₂ -C₁₂ alkoxywhich is interrupted by one or more oxygen atoms, unsubstituted or C₁-C₄ alkyl-substituted C₃ -C₁₂ cycloalkoxy, unsubstituted or C₁ -C₄alkoxy- and/or C₁ -C₄ alkyl-substituted phenoxy, unsubstituted or C₁ -C₄alkyl-substituted benzyloxy, tetrahydrofurfuryloxy, C₂ -C₆ alkenyloxy,--O--Si--(R₇)₃, C₁ -C₈ alkylthio, C₃ -C₈ cycloalkylthio, unsubstitutedor C₁ -C₄ alkyl- and/or C₁ -C₄ alkoxy-substituted benzylthio,unsubstituted or C₁ -C₄ alkyl- and/or C₁ -C₄ alkoxy-substitutedphenylthio, --S(O)R₈, --SO₂ R₈, --N(R₉)₂, ##STR8## where R₃ and R₄ arenot simultaneously hydrogen, and at least one radical R₃ or R₄ in the##STR9## radical is unsubstituted or C₅ -C₈ cycloalkyl- orphenoxy-substituted C₁ -C₁₂ alkoxy, C₂ -C₁₂ alkoxy which is interruptedby one or more oxygen atoms, unsubstituted or C₁ -C₄ alkyl-substitutedC₃ -C₁₂ cycloalkoxy, unsubstituted or C₁ -C₄ alkoxy- and/or C₁ -C₄alkyl-substituted phenoxy, unsubstituted or C₁ -C₄ alkyl-substitutedbenzyloxy, tetrahydrofurfuryloxy or C₂ -C₆ alkenyloxy, and in the casewhere Z is --NR₁₀ --, R₃ and R₄ are Cl, Br or I, the two R₆ radicals,independently of one another, are C₁ -C₄ alkyl or C₂ -C₁₀ alkenyl, orthe two R₆ radicals, together with the nitrogen atom to which they arebonded, form a morpholino radical,

R₇ is C₁ -C₁₂ alkyl, C₅ -C₈ cycloalkyl or unsubstituted or C₁ -C₆alkyl-substituted phenyl,

R₈ is unsubstituted or C₁ -C₄ alkyl-substituted phenyl or α-tertiary C₄-C₆ alkyl,

R₉ is unsubstituted or phenyl-, C₇ -C₁₂ alkylphenyl-, C₅ -C₈ cycloalkyl-or C₁ -C₄ alkyl-C₅ -C₈ cycloalkyl-substituted C₁ -C₈ alkyl, C₂ -C₈alkenyl, unsubstituted or C₁ -C₄ alkyl-substituted C₅ -C₈ cycloalkyl, C₆-C₂₀ cycloalkenylalkyl, unsubstituted or

C₁ -C₁₂ alkyl-substituted phenyl, a ##STR10## radical, where, inaddition, the two R₉ radicals in --N(R₉)₂ are identical or differentand, together with the nitrogen atom to which they are bonded, may forma 5- or 6-membered heterocyclic ring which, in addition to the nitrogenatom, may also contain further nitrogen, oxygen or sulfur atoms, or thetwo R₉ radicals, together with the nitrogen atom to which they arebonded, form a ##STR11## radical, R₁₀ is as defined for R₉ oradditionally is naphthyl, biphenylyl, pyridyl or pyrimidinyl, theseradicals being unsubstituted or substituted by Cl, Br, I, NO₂, C₁ -C₁₂alkyl, C₁ -C₁₀ alkoxy, C₁ -C₈ alkylthio, phenylthio, morpholino or--N(C₁ -C₄ alkyl)₂, or R₁₀ is phenyl which is substituted by Cl, Br, I,NO₂, C₁ -C₁₀ alkoxy, C₁ -C₈ alkylthio, phenylthio, morpholino or --N(C₁-C₄ alkyl)₂,

X os --O--, --S--, ##STR12## methylene or ethylene, and A is C₁ -C₁₂alkylene or --X--A--X-- is a direct bond.

The R₁ groups are preferably identical radicals. Suitable substituentsfor R₁ are: linear or branched alkyl or alkoxy having 1 to 18,particularly 1 to 12 and in particular 1 to 6 carbon atoms, and alkenylhaving 2 to 18, particularly 2 to 12, and in particular 2 to 6 carbonatoms, e.g. methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl,hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl andcorresponding alkenyl and alkoxy groups; cycloalkyl having 5 to 8 ringcarbon atoms, e.g. cyclopentyl, cyclohexyl, cycloheptyl,methylcyclopentyl and methylcyclohexyl; phenyl and naphthyl,phenyl-substituted C₁ -C₁₂ alkyl, e.g. benzyl and phenylethyl; cyano andCl, I and Br; --Si(R₂)₃ and --Ge(R₂)₃ in which R₂ is preferably C₁ -C₈alkyl, cyclohexyl, phenyl or benzyl. Examples of alkyl R₂ are methyl,ethyl, n- and i-propyl, n-, i- and t-butyl, pentyl, hexyl, heptyl andoctyl. The radicals R₁ may contain up to 5, but in particular up to 3substituents. The two R₁ groups are preferably cyclopentadienyl.sup.⊖ ormethylcyclopentadienyl.sup.⊖ radicals, in particularcyclopentadienyl.sup.⊖ radicals.

Any C₁ -C₁₂ alkyl radicals are, for example, linear or branched C₁ -C₁₂alkyl, preferably C₁ -C₈ alkyl, in particular C₁ -C₄ alkyl. Examples aremethyl, ethyl and the isomers of propyl, butyl, pentyl, hexyl, heptyl,octyl, nonyl, decyl, undecyl and dodecyl. Tertiary C₄ -C₆ alkyl is, forexample, t-butyl, 2-methylbut-2-yl, 2,3-dimethylbut-2-yl or2-methylpent-2-yl.

C₁ -C₁₂ Alkylene A is methylene, ethylene, propylene, butylene,pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecyleneor dodecylene, preferably ethylene or methylene.

Examples of C₁ -C₄ alkoxy-substituted C₁ -C₁₂ alkyl radicals aremethoxymethyl, ethoxymethyl, propoxyrnethyl, butoxymethyl, methoxyethyl,ethoxyethyl, butoxyethyl, propoxyethyl, methoxypropyl, ethoxypropyl,methoxybutyl, ethoxybutyl, methoxyhexyl, methoxyoctyl andmethoxydodecyl.

Phenyl-substituted C₁ -C₁₂ alkyl is, for example, benzyl,1,1-dimethylbenzyl, phenylethyl, phenylpropyl or phenylbutyl.

C₁ -C₄ Alkyl-C₅ -C₈ cycloalkyl is C₅ -C₈ cycloalkyl which is substitutedby C₁ -C₄ alkyl, e.g. methylcyclopentyl or methylcyclohexyl.

C₅ -C₈ Cycloalkyl is, for example, cyclopentyl, cyclohexyl, cycloheptylor cyclooctyl, preferably cyclopentyl or cyclohexyl.

Examples of C₇ -C₁₂ alkylphenyl-, C₅ -C₈ cycloalkyl- or C₁ -C₄ alkyl-C₅-C₈ -cycloalkyl-substituted C₁ -C₈ alkyl are methylbenzyl, ethylbenzyl,butylbenzyl, 2,6-dimethylbenzyl, 2,4,6-trimethylbenzyl,2,6-dimethylphenylethyl, -propyl or -butyl, 2,4,6-trimethylphenylethyl,-propyl or -butyl, 2,6-dimethylphenyl-α,α-dimethylethyl,2,4,6-trimethylphenyl-α,α-dimethylethyl, cyclopentyl- orcyclohexylmethyl, cyclopentyl- or cyclohexylethyl, cyclopentyl- orcyclohexylpropyl, cyclopentyl- or cyclohexylbutyl,(methylcyclopentyl)methyl, (ethylcylohexyl)methyl or -ethyl,(butylcyclopentyl)methyl, or (propylcyclohexyl)methyl or -ethyl.

α-Tertiary C₄ -C₆ alkyl is, for example, t-butyl, 1,1-dimethylprop-1-yl,1,1,2-trimethylprop-1-yl or 1,1 -dimethylbut-1-yl, preferably t-butyl.

Any C₃ -C₈ cycloalkyl substituents are, for example, cyclopropyl,cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl, in particularcyclopentyl or cyclohexyl, preferably cyclohexyl. C₁ -C₁₂Alkyl-substituted C₃ -C₈ cycloalkyl is, for example, methyl-, dimethyl-,ethyl-, n-propyl-, i-propyl-, n-butyl-, i-butyl-, t-butyl-, octyl- ordodecylcyclopentyl or -cyclohexyl.

C₆ -C₂₀ Cycloalkenylalkyl is, for example, cyclopentenyl-, cyclohexenyl-or cyclooctenylmethyl or -ethyl.

C₁ -C₁₂ Alkyl-, Cl-, Br-, I- or C₁ -C₄ alkoxy-substituted phenyl ismonosubstituted or polysubstituted, particularly monosubstituted totrisubstituted, in particular monosubstituted or disubstituted,preferably monosubstituted phenyl. Examples of such radicals are tolyl,mesityl, xylyl, ethylphenyl, butylphenyl, dodecylphenyl, methoxyphenyl,dimethoxyphenyl, ethoxyphenyl, diethoxyphenyl, butoxyphenyl,chlorophenyl, dichlorophenyl and trichlorophenyl. Alkyl and alkoxysubstituents on the phenyl substituent preferably have 1-4 carbon atoms.

C₁ -C₈ Alkylthio-, phenyl- or phenylthio-substituted phenyl R₃, R₄ or R₅is monosubstituted or polysubstituted, particularly monosubstituted totrisubstituted, in particular monosubstituted or disubstituted,preferably monosubstituted phenyl. The substituents are in the 3-, 4-,3,4- or 3,4,5-position, preferably in the 4-position, of the phenylring.

Any C₂ -C₁₂ alkenyl radicals are, for example, linear or branched C₂-C₁₂ alkenyl, preferably C₂ -C₈ alkenyl, in particular C₂ -C₄ alkenyl.The alkenyl may be monounsaturated or polyunsaturated. Examples areallyl, methallyl, 1,1-dimethylallyl, butenyl, hexenyl, octenyl,2,5,8-trimethylnona-2,7-dien-5-yl, undecenyl and dodecenyl, preferablyallyl and methallyl. C₂ -C₁₂ Alkenyl R₅ is, in particular,2,5,8-trimethylnona-2,7-dien-5-yl.

C₁ -C₁₂ Alkoxy is, for example, linear or branched. Preference is givento C₁ -C₈ alkoxy, in particular C₁ -C₆ alkoxy and particularly C₁ -C₄alkoxy. Examples are methoxy, ethoxy and the isomers of propoxy, butoxy,pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxyand dodecyloxy. C₂ -C₁₂ Alkoxy which is interrupted by one or moreoxygen atoms is, for example, the --O--CH₂ --OCH₃, --O--CH₂ --OC₂ H₅,--O--(CH₂ --O)_(x) --CH₃, --O--(CH₂ --O)_(x) --C₂ H₅, --O--(CH₂ CH₂--O)_(x) --CH₃ or --O--(CH₂ CH₂ --O)_(x) --C₂ H₅ group, where x is anumber from 1 to 20. C₂ -C₁₂ Alkoxy which is interrupted by oxygen atomsis in particular --O--CH₂ --OCH₃.

C₅ -C₈ Cycloalkyl-substituted C₁ -C₁₂ alkoxy is, for example,cyclohexylmethoxy, cyclopentylmethoxy, cyclohexylethoxy orcyclopentylethoxy, preferably cyclohexylmethoxy. Phenoxy-substituted C₁-C₁₂ alkoxy is, for example, phenoxymethoxy, phenoxyethoxy,phenoxybutoxy or phenoxyoctyloxy, preferably phenoxyethoxy.

C₃ -C₁₂ Cycloalkoxy is, for example, cyclopropoxy, cyclopentoxy,cyclohexyloxy, cycloheptyloxy, cyclooctyloxy or cyclododecyloxy, inparticular cyclopentoxy or cyclohexyloxy, preferably cyclohexyloxy. Ifthese radicals are substituted by C₁ -C₄ alkyl, they are monosubstitutedto tetrasubstituted, in particular monosubstituted to trisubstituted,preferably monosubstituted. These radicals are, for example,methylcyclohexyloxy, methylcyclopentyloxy, dimethylcyclohexyloxy,ethylcyclohexyloxy, diethylcyclohexyloxy, propylcyclohexyloxy orbutylcyclohexyloxy.

C₁ -C₄ Alkoxy-substituted phenoxy is monosubstituted totetrasubstituted, in particular monosubstituted to trisubstituted,preferably monosubstituted or disubstituted. Examples of such radicalsare 2,6-dimethoxyphenoxy, 2,4-dimethoxyphenoxy, 2,4,6-trimethoxyphenoxy,4-methoxyphenoxy, 2-methoxyphenoxy, 6-methoxyphenoxy,2,6-diethoxyphenoxy, 2,4-diethoxyphenoxy, 2-ethoxyphenoxy,4-ethoxyphenoxy, 6-ethoxyphenoxy, propoxyphenoxy or butoxyphenoxy.

C₁ -C₄ Alkyl-substituted phenoxy is monosubstituted to tetrasubstituted,in particular monosubstituted to trisubstituted, preferablymonosubstituted or disubstituted. Examples of such radicals are2,6-dimethylphenoxy, 2,4-dimethylphenoxy, 2,4,6-trimethylphenoxy,4-methylphenoxy, 2-methylphenoxy, 6-methylphenoxy, 2,6-diethylphenoxy,2,4-diethylphenoxy, 2-ethylphenoxy, 4-ethylphenoxy, 6-ethylphenoxy,propylphenoxy or butylphenoxy.

C₁ -C₄ Alkyl-substituted benzyloxy is monosubstituted totetrasubstituted, in particular monosubstituted to trisubstituted,preferably monosubstituted or disubstituted. The alkyl substituents maybe positioned both on the methylene and on the aromatic ring of thebenzyloxy radical. Examples of such radicals are 2-methylbenzyloxy,4-methylbenzyloxy, 6-methylbenzyloxy, 2,4-dimethylbenzyloxy,2,6-dimethylbenzyloxy, 2,6-diethylbenzyloxy, 2,4-diethylbenzyloxy,propylbenzyloxy, butylbenzyloxy, 1-methyl-1-phenylmethoxy,1,1-dimethyl-1-phenylmethoxy or 1-methyl-1-(2,6-dimethylphenyl)-methoxy.

C₂ -C₆ Alkenyloxy contains, for example, linear or branched alkenylradicals. Preference is given to C₂ -C₄ alkenyloxy- Examples areallyloxy, methallyloxy, 1,1-dimethylallyloxy, butenyloxy, hexenyloxy,octenyloxy, undecenyloxy and dodecenyloxy, preferably allyloxy andmethallyloxy.

Any C₁ -C₈ alkylthio substituents are, for example, methylthio,ethylthio or isomers of propylthio, butylthio, pentylthio, hexylthio,heptylthio or octylthio. Preference is given to C₁ -C₆ alkylthio, inparticular C₁ -C₄ alkylthio, for example i-butylthio. C₃ -C₈Cycloalkylthio is C₃ -C₈ cycloalkyl-S-, where the cycloalkyl radicalsare defined as described above apart from the corresponding number ofcarbon atoms. Substituted benzylthio and phenylthio may be, for example,monosubstituted to trisubstituted, for example monosubstituted ordisubstituted, in particular monosubstituted, by C₁ -C₄ alkoxy and/or C₁-C₄ alkyl. Examples are (4-methyl)-, (2,4-dimethyl)-,(2,4,6-trimethyl)-, (4-methoxy)-, (2,4-dimethoxy)-, (2,4,6-trimethoxy)-,(4-ethoxy)-, (2,4-diethoxy)-, (2,4,6-trimethoxy)-,(4-methoxy-2-methyl)-, (2,4-dimethoxy-6-methyl)-, (4-ethoxy-2-methyl)-,(2,4-diethoxy-6-methyl)benzylthio or -phenylthio.

Halogen is chlorine, bromine or iodine, in particular chlorine orbromine, preferably chlorine.

If the two R₉ radicals in --N(R₉)₂, together with the nitrogen atom towhich they are bonded, form a 5- or 6-membered heterocyclic ring which,in addition to the nitrogen atom, may also contain further nitrogen,oxygen or sulfur atoms, these rings may be saturated or preferablyunsaturated. They are, for example, pyrryl, dimethylpyrryl, piperidinyl,morpholinyl, piperazinyl, 4-methylpiperazinyl, diazolyl, thienyl,thiazolyl, imidazolyl or oxazolyl radicals.

--N(C₁ -C₄ Alkyl)₂ is, for example, dimethylamino, diethylamino,dipropylamino, dibutylamino or methylethylamino, in particularlydimethylamino.

R₅ is, for example, C₁ -C₁₂ alkyl, preferably C₁ -C₈ alkyl, for exampleC₁ -C₆ alkyl, in particular C₁ -C₄ alkyl, C₃ -C₈ cycloalkyl, inparticular cyclohexyl or cyclopentyl, or adamantyl.

If R₅ is, for example, phenyl which is substituted by --NR₈ R₉, R₈ andR₉ are preferably identical and are C₁ -C₄ alkyl, in particular methyl.

Substituted phenyl R₁₀ is phenyl which is monosubstituted orpolysubstituted, particularly monosubstituted to trisubstituted, inparticular monosubstituted or disubstituted, preferably monosubstitutedphenyl. Examples of such radicals are tolyl, mesityl, xylyl,ethylphenyl, butylphenyl, dodecylphenyl, methoxyphenyl, dimethoxyphenyl,ethoxyphenyl, diethoxyphenyl, butoxyphenyl, chlorophenyl,dichlorophenyl, trichlorophenyl, morpholinophenyl anddimethylaminophenyl. Alkyl substituents on the phenyl substituentpreferably have 1-4 carbon atoms.

The compounds of the formula I are generally prepared by reacting atitanocene dihalide with the radical Q in the presence of a strong base:##STR13## R₁, Q and n are as defined in claim 1. Y is chlorine, bromineor iodine, and T is hydrogen or bromine.

Titanocenes where Y=CN or SCN are prepared by substitution reactionsfrom the corresponding titanocene where Y=Cl.

Titanocenes where Y=--O--CO--CH₃, --O--C--phenyl or --O--SO₂ --CH₃ areprepared analogously to the method described in U.S. Pat. No. 4,713,401for fluorine-containing titanocenes.

The compounds of the formula I (3) in which Q is a pyrimidine radicalare prepared, for example, by reacting a titanocene dihalide (1) with asubstituted pyrimidine (2) in the presence of a strong base: ##STR14##(n, R₁, R₃, R₄ and R₅ are as defined in the claims, T is hydrogen or Br,and Y is Cl, Br or I). Reactions of this type have been described, forexample, by M. D. Mehta, D. Miller and M. F. Mooney in J. Chem. Soc.(1965), 6695. Further information on such reactions is given by D. J.Brown, The Pyrimidines, Suppl. 1, 159, or Suppl. 2, 219, Intersciencepublishers, John Wiley & Sons, New York/London, 1962.

In the reactions described above, the bases used can also be, forexample, s-butyllithium, t-butyllithium or magnesium metal.

In the preparation of the titanocenes containing tris-ether pyrimidineradicals (R₃, R₄ and R₅ =--OR), it should be noted that T in thecompound (2) must be Br, since the corresponding unbrominated tris-etherpyrimidine is not directly deprotonated by butyllithium. Thecorresponding pyrimidine is thus brominated in the 5-position before thereaction with butyllithium and the (R₁)₂ --TiY₂ (cf. J. Chem. Soc. 1965,5467-73).

U.S. Pat. No. 5,075,467 describes a process for the preparation offluorinated titanocenes in which a titanocene dihalide is reacted with afluorinated and possibly additionally substituted phenyl in the presenceof lithium amide at from -30° to +25° C. It is, for example, alsopossible to prepare the compounds according to the invention analogouslyto this process.

The pyrimidine compounds (2) can be obtained, for example, bychlorinating barbituric acid using POCl₃ and then reacting thechlorinated product with sodium alkoxides. Selection of the appropriatestoichiometry and reaction conditions allows the dichloromonoether,monochlorodiether or trisether compounds to be obtained (cf. J. Baddileyand A. Tapham, J. Chem. Soc. 1944, 679, and D. J. Brown, ThePyrimidines, Chapter IV, 202, Interscience publishers, John Wiley &Sons, New York/London 1962). Synthesis of 4,6-dichloro-2-arylpyrimidinesis described, for example, by J. A. Hendry and R. F. Homer in J. Chem.Soc. (1952), 328-333.

The compounds (2) containing thioether radicals are prepared by reactingthe corresponding chlorine-substituted pyrimidines with thecorresponding mercaptans in the presence of a base, preferably sodiumhydride. An example of the preparation of a compound of this typecontaining the thioether radical in the 2-position is: ##STR15## R₃ andR₄ are as defined above, and R is C₁ -C₈ alkyl, or unsubstituted orsubstituted benzyl or phenyl.

The corresponding compounds containing a sulfone radical are prepared,for example, from the above-described alkylthioether compounds byoxidation using m-chloroperbenzoic acid.

2-Alkylpyrimidines can be prepared, for example, from alkyl nitriles viaalkylamidines by the method described by D. J. Brown in Australian J.Chem., (1977) 30, 1785-1791. ##STR16##

The pyrimidines containing ##STR17## substituents are prepared, forexample, by reacting a chlorinated pyrimidine with a secondary amine andthen N-acylating the product. ##STR18##

Another possibility is to start, for example, from an aminopyrimidine,which is first alkylated and then acylated. ##STR19## (Hal is halogen,and R₄, R₅, R₈ and R₉ are as defined above).

The preparation of chlorinated pyrimidines and aminopyrimidines is knownin general terms.

The preparation of five-membered rings containing two hetero atoms##STR20## in which R₃, R₄ and Z are as defined above, is known ingeneral terms to persons skilled in the art and is described in a numberof publications, such as, for example, J. Chem. Soc. C (1968), 466;Synthetic Commun. 20 (1990), 3213-3218; Izv. Akad. Nauk, SSSR, Ser.Khim. (1990) 3, 640, 645; Bull. Chem. Soc. Jpn (1991) 2, 719-20;Synthetic Comm. 20 (1990), 3161-3166; Synthetic Comm. 20 (1990),2799-2804; J. Chem. Soc., Chem. Comm. (1991), 17-18; Can. J. Chem. 69(1991), 625-631; Advances in Heterocyclic Chemistry (1979) 25, 154, 159,171; J. Chem. Soc. C (1968), 172; Chem. Pharm. Bulletin 16 (1968), 148or the reviews by A. N. Kost and I. J. Grandberg in Advances inHeterocyclic Chemistry (1966) 6, 370ff; B. J. Wakefield und D. J. Wrightin Advances in Heterocyclic Chemistry (1979) 25, 148ff or K. R. H.Wooldridge Advances in Heterocyclic Chemistry (1972) 14, 12, 20, 29.

The starting materials (IV) for the preparation of compounds of theformula II in which X is --O-- or --S-- can be prepared, for example, byreacting 2 equivalents of a substituted pyrimidine with one equivalentof an alkylenediol or alkylenethiol in the presence of 2 equivalents ofa base: ##STR21##

The starting materials (V) for the preparation of compounds of theformula II in which X is ##STR22## can be obtained, for example, byreacting 2 equivalents of a substituted pyrimidine with one equivalentof the corresponding bisaminoalkylene in the presence of 2 equivalentsof a base and subsequently acylating the product: ##STR23##

The starting materials (VI) for the preparation of compounds of theformula II in which X is methylene, ethylene or a direct bond is carriedout, for example, by reacting one equivalent of the correspondingtetraketone with two equivalents of an amidine: ##STR24##

The compounds of the formula II are then prepared analogously to thecompounds of the formula I by reaction with (R₁)₂ TiY₂ by replacing thepyrimidine used with the corresponding compound of the formula IV, V orVI. The reactants are expediently employed here in a ratio of 1:1.

Also interesting are compounds of the formula ##STR25## (I) in whichboth R₁ radicals are, independently of one another,cyclopentadienyl.sup.⊖, indenyl.sup.⊖ or4,5,6,7-tetrahydroindenyl.sup.⊖, these radicals being unsubstituted orsubstituted by C₁ -C₁₈ alkyl, C₁ -C₁₈ alkoxy, C₂ -C₁₈ alkenyl, C₅ -C₈cycloalkyl, C₁ -C₄ alkyl-C₅ -C₈ cycloalkyl, phenyl, naphthyl,phenyl-substituted C₁ -C₁₂ alkyl, --Si(R₂)₃, --Ge(R₂)₃, cyano, Cl, Br orI, and

the two R₂ radicals, independently of one another, are C₁ -C₁₂ alkyl, C₅-C₈ cycloalkyl, or unsubstituted or C₁ -C₆ alkyl-substituted phenyl orbenzyl, ##STR26## radical, Z is --NR₁₀ --, --O-- or --S--,

Y is Cl, Br, I, CN, SCN or --O--SO₂ --CH₃,

n is 1 or2,

m is 0 or 1, where the sum of n and m must be 2,

R₃, R₄ and R₅, independently of one another, are hydrogen, Cl, Br, I,unsubstituted or C₁ -C₄ alkoxy- or phenyl-substituted C₁ -C₁₂ alkyl,unsubstituted or C₁ -C₄ alkyl-substituted C₃ -C₈ cycloalkyl,unsubstituted or C₁ -C₁₂ alkyl-, Cl-, Br-, I-, C₁ -C₈ alkylthio-, --NR₈R₉ -- or C₁ -C₁₀ alkoxy-substituted phenyl, pyrryl, furyl, thienyl,imidazolyl or pyridyl, or R₃, R₄ and R₅ are unsubstituted C₂ -C₁₂alkenyl or C₂ -C₁₂ alkenyl which is substituted by unsubstituted or C₁-C₄ alkyl-, C₁ -C₄ alkoxy-, C₁ -C₄ alkylthio-, Cl-, Br- or I-substitutedphenyl or ##STR27## or R₃, R₄ and R₅ are unsubstituted or C₅ -C₈cycloalkyl-substituted C₁ -C₁₂ alkoxy, C₂ -C₁₂ alkoxy which isinterrupted by one or more oxygen atoms, unsubstituted or C₁ -C₄alkyl-substituted C₃ -C₁₂ cycloalkoxy, unsubstituted or C₁ -C₄ alkoxy-or C₁ -C₄ alkyl-substituted phenoxy, unsubstituted or C₁ -C₄alkyl-substituted benzyloxy, tetrahydrofurfuryloxy, C₂ -C₆ alkenyloxy,--O--Si--(R₇)₃, C₁ -C₈ alkylthio, C₃ -C₈ cycloalkylthio, unsubstitutedor C₁ -C₄ alkyl- and/or C₁ -C₄ alkoxy-substituted benzylthio,unsubstituted or C₁ -C₄ alkyl- and/or

C₁ -C₄ alkoxy-substituted thiophenyl, --S(O)R₈, --SO₂ R₈, --N(R₉)₂,##STR28## where R₃ and R₄ are not simultaneously hydrogen, and at leastone radical R₃ or R₄ in the ##STR29## radical is unsubstituted or C₅ -C₈cycloalkyl-substituted C₁ -C₁₂ alkoxy, C₂ -C₁₂ alkoxy which isinterrupted by one or more oxygen atoms, unsubstituted or C₁ -C₄alkyl-substituted C₃ -C₁₂ cycloalkoxy, unsubstituted or C₁ -C₄ alkoxy-or C₁ -C₄ alkyl-substituted phenoxy, unsubstituted or C₁ -C₄alkyl-substituted benzyloxy, tetrahydrofurfuryloxy or C₂ -C₆ alkenyloxy,and in the case where Z is --NR₁₀ --, R₃ and R₄ are Cl, Br or I, the twoR₆ radicals, independently of one another, are C₁ -C₄ alkyl or C₂ -C₁₀alkenyl, or the two R₆ radicals, together with the nitrogen atom towhich they are bonded, form a morpholino radical,

R₇ is C₁ -C₁₂ alkyl, C₅ -C₈ cycloalkyl or unsubstituted or C₁ -C₆alkyl-substituted phenyl,

R₈ is unsubstituted or C₁ -C₄ alkyl-substituted phenyl or α-tertiary C₄-C₆ alkyl,

R₉ is unsubstituted or phenyl-, C₇ -C₁₂ alkylphenyl-, C₅ -C₈ cycloalkyl-or C₁ -C₄ alkyl-C₅ -C₈ cycloalkyl-substituted C₁ -C₈ alkyl, C₂ -C₈alkenyl, unsubstituted or C₁ -C₄ alkyl-substituted C₅ -C₈ cycloalkyl, C₆-C₂₀ cycloalkenylalkyl, unsubstituted or

C₁ -C₁₂ alkyl-substituted phenyl, a ##STR30## radical, where, inaddition, the two R₉ radicals in --N(R₉)₂ are identical or differentand, together with the nitrogen atom to which they are bonded, may forma 5- or 6-membered heterocyclic ring which, in addition to the nitrogenatom, may also contain further nitrogen, oxygen or sulfur atoms, or, ifthe two R₉ radicals are a ##STR31## group, the two R₉ radicals, togetherwith the nitrogen atom to which they are bonded, form a ##STR32##radical, R₁₀ is as defined for R₉, and

if n=2, the formula I also includes compounds of the formula II##STR33## in which X is --O--, --S--, ##STR34## methylene or ethylene,and A is C₁ -C₁₂ alkylene or --X--A--X-- is a direct bond.

Preference is given to compounds of the formulae I and II in which bothR₁ radicals, independently of one another, are cyclopentadienyl.sup.⊖which is unsubstituted or substituted by C₁ -C₁₈ alkyl, C₁ -C₁₈ alkoxy,C₂ -C₁₈ alkenyl, --Si(R₂)₃ or Cl, Br, I, in particular C₁ -C₄ alkyl.

Further interesting compounds of the formulae I and II are those inwhich R₃ and R₅ are unsubstituted or C₅ -C₈ cycloalkyl- orphenoxy-substituted C₁ -C₁₂ alkoxy, C₂ -C₁₂ alkoxy which is interruptedby one or more oxygen atoms, unsubstituted or C₁ -C₄ alkyl-substitutedC₃ -C₁₂ cycloalkoxy, unsubstituted or C₁ -C₄ alkoxy- and/or C₁ -C₄alkyl-substituted phenoxy, unsubstituted or C₁ -C₄ alkyl-substitutedbenzyloxy, tetrahydrofurfuryloxy or C₂ -C₆ alkenyloxy.

Particular preference is given to compounds in which R₃ and R₅ areunsubstituted or cyclohexyl- or phenoxy-substituted C₁ -C₁₂ alkoxy, C₂-C₁₂ alkoxy which is interrupted by one or more oxygen atoms,unsubstituted or C₁ -C₄ alkyl-substituted C₅ -C₈ cycloalkoxy,unsubstituted or C₁ -C₄ alkoxy-substituted phenoxy, unsubstituted or C₁-C₄ alkyl-substituted benzyloxy, tetrahydrofurfuryl or C₂ -C₆alkenyloxy.

Also interesting are compounds of the formulae I and II in which R₅ isC₁ -C₈ alkylthio, C₃ -C₈ cycloalkylthio, unsubstituted or C₁ -C₄ alkyl-and/or C₁ -C₄ alkoxy-substituted benzylthio, unsubstituted or C₁ -C₄alkyl- and/or C₁ -C₄ alkoxy-substituted phenylthio, --S(O)R₈ or --SO₂R₈, in particular C₁ -C₈ akylthio.

Particularly interesting compounds are those in which Q is a ##STR35##radical.

Preference is also given to compounds in which R₄ is Cl, Br or I, inparticular Cl.

Further preferred compounds of the formula I are those in which n=2 andm=0.

Also interesting are compounds of the formula I in which n and m are 1.

Preference is also given to compounds of the formula I in which Y is Cl,Br or I, in particular Cl.

Other preferred compounds are those in which R₃, R₄ and R₅,independently of one another, are unsubstituted or C₅ -C₈ cycloalkyl- orphenoxy-substituted C₁ -C₁₂ alkoxy, C₂ -C₁₂ alkoxy which is interruptedby one or more oxygen atoms, unsubstituted or C₁ -C₄ alkyl-substitutedC₃ -C₁₂ cycloalkoxy, unsubstituted or C₁ -C₄ alkoxy- and/or C₁ -C₄alkyl-substituted phenoxy, unsubstituted or C₁ -C₄ alkyl-substitutedbenzyloxy, tetrahydrofurfuryloxy or C₂ -C₆ alkenyloxy.

In further interesting compounds of the formulae I and II, R₅ is phenyl,pyrryl, furyl, thienyl, imidazolyl, pyridyl, naphthyl, anthryl,phenanthryl or biphenylyl, where the radicals phenyl, pyrryl, furyl,thienyl, imidazolyl, pyridyl, naphthyl, anthryl, phenanthryl andbiphenylyl are unsubstituted or substituted by C₁ -C₁₂ alkyl,cyclopentyl, cyclohexyl, Cl, Br, I, C₁ -C₈ alkylthio, --NR₈ R₉, phenyl,phenylthio or C₁ -C₁₀ alkoxy.

Other important compounds are those in which R₃ is unsubstituted or C₅-C₈ cycloalkyl- or phenoxy-substituted C₁ -C₁₂ alkoxy, C₂ -C₁₂ alkoxywhich is interrupted by one or more oxygen atoms, unsubstituted or C₁-C₄ alkyl-substituted C₃ -C₁₂ cycloalkoxy, unsubstituted or C₁ -C₄alkoxy- and/or C₁ -C₄ alkyl-substituted phenoxy, unsubstituted or C₁ -C₄alkyl-substituted benzyloxy, tetrahydrofurfuryloxy or C₂ -C₆ alkenyloxy,

R₄ is Cl, and

R₅ is phenyl which is unsubstituted or substituted by C₁ -C₁₂ alkyl, Cl,Br, C₁ -C₈ alkylthio, --NR₈ R₉, phenyl, phenylthio or C₁ -C₁₀ alkoxy.

Likewise interesting are the compounds in which R₃ is unsubstituted orC₅ -C₈ cycloalkyl- or phenoxy-substituted C₁ -C₁₂ alkoxy, C₂ -C₁₂ alkoxywhich is interrupted by one or more oxygen atoms, unsubstituted or C₁-C₄ alkyl-substituted C₃ -C₁₂ cycloalkoxy, unsubstituted or C₁ -C₄alkoxy- and/or C₁ -C₄ alkyl-substituted phenoxy, unsubstituted or C₁ -C₄alkyl-substituted benzyloxy, tetrahydrofurfuryloxy or C₂ -C₆ alkenyloxy,

R₄ is Cl, and

R₅ is C₁ -C₁₂ alkyl, C₃ -C₈ cycloalkyl or adamantyl.

Particular mention should be made of compounds of the formula I in which

Y is Cl, --O--CO--CH₃ or --O--CO--phenyl,

R₃ is unsubstituted or C₅ -C₈ cycloalkyl- or phenoxy-substituted C₁ -C₁₂alkoxy, C₂ -C₁₂ alkoxy which is interrupted by one or more oxygen atoms,C₅ -C₈ cycloalkoxy, benzyloxy, tetrahydrofurfuryloxy or Cl,

R₄ is as defined for R₃ or additionally hydrogen, and

R₅ is as defined for R₃ or additionally hydrogen, C₁ -C₁₂ alkyl, C₁ -C₈alkylthio, pyrryl, or phenyl which is unsubstituted or substituted byCl, C₁ -C₁₀ alkoxy, phenyl, C₁ -C₈ alkylthio, phenylthio or --NR₈ R₉,and

R₁₀ is phenyl.

Preference is given to compounds of the formula I.

Particular mention should also be made of compounds of the formula I inwhich Q is ##STR36##

Preferred compounds of the formula I in which Q is ##STR37## are thosein which R₃ and R₄ are Cl,

Z is --NR₁₀ --, and

R₁₀ is phenyl which is unsubstituted or substituted by Cl, Br, I, NO₂,C₁ -C₁₂ alkyl, C₁ -C₁₀ alkoxy, C₁ -C₈ alkylthio, phenylthio, morpholinoor --N(C₁ -C₄ alkyl)₂.

The compounds of the formulae I and II according to the invention may,due to certain substituents, be in the form of a number of differentconformational isomers. The invention covers all conformational is, omenformed.

The compounds of the formulae I and II can be used according to theinvention as photoinitiators for the photopolymerisation ofethylenically unsaturated compounds or mixtures which contain suchcompounds.

This use may also take place in combination with another photoinitiatorand/or other additives.

The invention therefore also relates to photopolymerisable compositionscomprising

(a) at least one ethylenically unsaturated photopolymerisable compoundand

(b), as photoinitiator, at least one compound of the formula I or II, italso being possible for the composition to contain anotherphotoinitiator (c) and/or other additives.

Examples of suitable photoinitiators (c) are those of the titanocenetype which do not conform to the formula I or II, benzoin alkyl ethers,benzophenones, benzil ketals, 4-aroyl- 1,3-dioxolanes,dialkoxyacetophenones, α-hydroxy- or α-aminoacetophenones,α-hydroxycycloalkyl phenyl ketones, mono- or bisacylphosphine oxides, ormixtures thereof.

Mixtures of these photoinitiators (c) with titanocenes are described,for example, in EP-A-242 330 and U.S. Pat. No. 4,960,746. The noveltitanocenes of the formulae I and II according to the invention maylikewise be used as the titanocene component in the mixtures describedtherein.

If, in addition to the photoinitiator (b), the compositions according tothe invention also contain one or more further photoinitiators (c), theweight ratio between the two components (c) and (b) can be, for example,from 1:1 to 30:1, preferably from 5:1 to 15:1.

The unsaturated compounds can contain one or more olefinic double bonds.They can be of low molecular weight (monomeric) or relatively highmolecular weight (oligomeric). Examples of monomers containing onedouble bond are alkyl or hydroxyalkyl acrylates or methacrylates, e.g.methyl, ethyl, butyl, 2-ethylhexyl and 2-hydroxyethyl acrylate,isobornyl acrylate and methyl and ethyl methacrylate. Also interestingare silicone acrylates. Further examples are acrylonitrile, acrylamide,methacrylamide, N-substituted (meth)acrylamides, vinyl esters, such asvinyl acetate, vinyl ethers, such as isobutyl vinyl ether, styrene,alkyl- and halostyrenes, N-vinylpyrrolidone, vinyl chloride andvinylidene chloride.

Examples of monomers containing more than one double bond are ethyleneglycol diacrylate, propylene glycol diacrylate, neopentyl glycoldiacrylate, hexamethylene glycol diacrylate, bisphenol A diacrylate,4,4'-bis(2-acryloyloxymethoxy)diphenylpropane, trimethylolpropanetriacrylate, pentaerythritol triacrylate and tetraacrylate, vinylacrylate, divinylbenzene, divinyl succinate, diallyl phthalate, triallylphosphate, triallyl isocyanurate and tris(2-acryloylethyl)isocyanurate.

Examples of relatively high-molecular-weight (oligomeric),polyunsaturated compounds are acrylated epoxy resins, acrylated or vinylether- or epoxy-groups containing polyesters, polyurethanes andpolyethers. Further examples of unsaturated oligomers are unsaturatedpolyester resins, which are usually prepared from maleic acid, phthalicacid and one or more diols and have molecular weights of from about 500to 3000. In addition vinylether-monomers and -oligomers, as well asmaleat-terminated oligomers with polyester-, polyurethane-, polyether-,polyvinyl ether- and epoxy-main chains can be used. Especiallycombinations of oligomers containing vinylether groups and polymers, asare described in WO 90/01512, are suitable. Copolymers of monomersfunctionalized with vinylether or maleic acid are suitable, too.Unsaturated oligomers of this type can also be termed prepolymers.

Particularly suitable compounds are, for example, esters ofethylenically unsaturated carboxylic acids and polyols or polyepoxides,and polymers containing ethylenically unsaturated groups in the chain orin side groups, e.g. unsaturated polyesters, polyamides andpolyurethanes, and copolymers thereof, polybutadiene and butadienecopolymers, polyisoprene and isoprene copolymers, polymers andcopolymers containing (meth)acrylic groups in side chains, and mixturesof one or more of such polymers.

Examples of unsaturated carboxylic acids are acrylic acid, methacrylicacid, crotonic acid, itaconic acid, cinnamic acid, unsaturated fattyacids, such as linolenic acid or oleic acid. Preference is given toacrylic and methacrylic acids.

Suitable polyols are aromatic and in particular aliphatic andcycloaliphatic polyols. Examples of aromatic polyols are hydroquinone,4,4'-dihydroxybiphenyl, 2,2-di(4-hydroxyphenyl)propane, and novolaks andresols. Examples of polyepoxides are those based on said polyols, inparticular the aromatic polyols, and epichlorohydrin. Other suitablepolyols are polymers and copolymers containing hydroxyl groups in thepolymer chain or in side groups, e.g. polyvinyl alcohol and copolymersthereof, or hydroxyalkyl polymethacrylates or copolymers thereof. Othersuitable polyols are oligoesters containing hydroxyl terminal groups.

Examples of aliphatic and cycloaliphatic polyols are alkylenediols,preferably having 2 to 12 carbon atoms, such as ethylene glycol, 1,2-and 1,3-propanediol, 1,2-, 1,3- and 1,4-butanediol, pentanediol,hexanediol, octanediol, dodecanediol, diethylene glycol, triethyleneglycol, polyethylene glycols having molecular weights of, preferably,200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3-and 1,4-cyclohexanediol,1,4-dihydroxymethylcyclohexane, glycerol, tris(β-hydroxyethyl)amine,trimethylolethane, trimethylolpropane, pentaerythritol,dipentaerythritol and sorbitol.

The polyols may be partially or fully esterified with one or more thanone unsaturated carboxylic acid, where the free hydroxyl groups inpartial esters may, for example, be etherified or esterified with othercarboxylic acids.

Examples of esters are: trimethylolpropane triacrylate,trimethylolethane triacrylate, trimethylolpropane trimethacrylate,trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate,triethylene glycol dimethacrylate, tetraethylene glycol diacrylate,pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritoltetraacrylate, dipentaerythritol diacrylate, dipentaerythritoltriacrylate, dipentaerythritol tetraacrylate, dipentaerythritolpentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritoloctaacrylate, pentaerythritol dimethacrylate, pentaerythritoltrimethacrylate, dipentaerythritol dimethacrylate, dipentaerythritoltetramethacrylate, tripentaerythritol octamethacrylate, pentaerythritoldiitaconate, dipentaerythritol trisitaconate, dipentaerythritolpentaitaconate, dipentaerythritol hexaitaconate, ethylene glycoldiacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate,1,4-butanediol diitaconate, sorbitol triacrylate, sorbitoltetraacrylate, modified pentaerythritol triacrylate, sorbitoltetramethacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate,oligoester acrylates and methacrylates, glycerol diacrylate andtriacrylate, 1,4-cyclohexane diacrylate, and bisacrylates andbismethacrylates of polyethylene glycol having molecular weights of from200 to 1500, or mixtures thereof.

Suitable compounds as component (a) are also the amides of identical ordifferent unsaturated carboxylic acids of aromatic, cycloaliphatic andaliphatic polyamines, preferably having 2 to 6, in particular 2 to 4,amino groups. Examples of such polyamines are ethylenediamine, 1,2- and1,3-propylenediamine, 1,2-, 1,3- and 1,4-butylenediamine,1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine,dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine,phenylenediamine, bisphenylenediamine, di-(β-aminoethyl ether,diethylenetriamine, triethylenetetramine, di(β-aminoethoxy)- anddi(β-aminopropoxy)ethane. Other suitable polyamines are polymers andcopolymers, if desired with additional amino groups in the side chainand oligoamides containing amino terminal groups. Examples ofunsaturated amides of this type are: methylenebisacrylamide,1,6-hexamethylenebisacrylamide, diethylenetriaminetrismethacrylamide,bis(methacrylamidopropoxy)ethane, β-methacrylamidoethyl methacrylate,N[(β-hydroxyethoxy)ethyl]acrylamide.

Suitable unsaturated polyesters and polyamides are derived, for example,from maleic acid and diols or diamines. Some of the maleic acid may bereplaced by other dicarboxylic acids. They can be employed together withethylenically unsaturated comonomers, e.g. styrene. The polyesters andpolyamides may also be derived from dicarboxylic acids and ethylenicallyunsaturated diols or diamines, in particular relatively long-chain diolsor diamines having, for example, 6 to 20 carbon atoms. Examples ofpolyurethanes are those built up from saturated or unsaturateddiisocyanates and unsaturated or saturatediols.

Polybutadiene and polyisoprene and copolymers thereof are known.Examples of suitable comonomers are olefins, such as ethylene, propene,butene, hexene, (meth)acrylates, acrylonitrile, styrene and vinylchloride. Polymers containing (meth)acrylate groups in the side chainare likewise known. These may be, for example, products of the reactionof novolak-based epoxy resins with (meth)acrylic acid, homopolymers orcopolymers of vinyl alcohol or hydroxyalkyl derivatives thereof whichhave been esterified by means of (meth)acrylic acid, or homopolymers andcopolymers of (meth)acrylates which have been esterified by means ofhydroxyalkyl (meth)acrylates.

The photopolymerisable compounds can be employed alone or in any desiredmixtures. Preference is given to mixtures of polyol (meth)acrylates.

It is also possible to add binders to the compositions according to theinvention, which is particularly expedient if the photopolymerisablecompounds are liquid or viscous substances. The amount of binder can be,for example, 5-95% by weight, preferably 10-90% by weight, in particular40-90% by weight, based on the total solids content. The choice ofbinder depends on the area of application and the properties requiredtherefor, such as developability in aqueous or organic solvent systems,adhesion to substrates and oxygen sensitivity.

Examples of suitable binders are polymers having a molecular weight ofabout 5000-2,000,000, preferably 10,000-1,000,000. Examples are:homopolymers and copolymers of acrylates and methacrylates, e.g.copolymers of methyl methacrylate-ethyl acrylate-methacrylic acid,poly(alkyl methacrylates), poly (alkyl acrylates); cellulose esters andethers, such as cellulose acetate, cellulose acetate butyrate,methylcellulose and ethylcellulose; polyvinyl butyral, polyvinylformal,cyclised rubber, polyethers, such as polyethylene oxide, polypropyleneoxide and polytetrahydrofuran; polystyrene, polycarbonate, polyurethane,chlorinated polyolefins, polyvinyl chloride, copolymers of vinylchloride-vinylidene chloride, copolymers of vinylidene chloride withacrylonitrile, methyl methacrylate and vinyl acetate, polyvinyl acetate,copoly(ethylene/vinyl acetate), polymers such as polycaprolactam andpoly(hexamethyleneadipamide) and polyesters, such as poly(ethyleneglycol terephthalate) and poly(hexamethylene glycol succinate).

The unsaturated compounds can also be used as a mixture withnon-photopolymerisable, film-forming components. These may be, forexample, physically drying polymers or solutions thereof in organicsolvents, e.g. nitrocellulose or cellulose acetobutyrate. However, theymay also be chemically or thermally curable resins, e.g.polyisocyanates, polyepoxides or melamine resins. The additional use ofthermally curable resins is important for use in so-called hybridsystems, which are photopolymerised in a first step and crosslinked bythermal aftertreatment in a second step.

In addition to the photoinitiator, the photopolymerisable mixtures mayalso contain various additives. Examples are thermal inhibitors, whichare intended to prevent premature polymerisation, e.g. hydroquinone,hydroquinone derivatives, p-methoxyphenol, β-naphthol or stericallyhindered phenols, e.g. 2,6-di(tert-butyl)-p-cresol. The shelf life inthe dark can be increased by using, for example, copper compounds, suchas copper naphthenate, stearate or octanoate, phosphorus compounds, e.g.triphenylphosphine, tributylphosphine, triethyl phosphite, triphenylphosphite or tribenzyl phosphite, quaternary ammonium compounds, e.g.tetramethylammonium chloride or trimethylbenzylammonium chloride, orhydroxylamine derivatives, e.g. N-diethylhydroxylamine. Atmosphericoxygen can be excluded during the polymerisation by adding paraffin orsimilar wax-like substances, which, on commencement of thepolymerisation, migrate to the surface due to low solubility in thepolymer and form a transparent surface layer which prevents contact withair. As light stabilisers, UV absorbers, e.g. those of thebenzotriazole, benzophenone, oxanilide or hydroxyphenyl-s-triazine type,can be added in small amounts. Still better is the addition of lightstabilisers which do not absorb UV light, e.g. sterically hinderedamines (HALS).

The photopolymerisation can be accelerated by adding amines, e.g.triethanolamine, N-methyldiethanolamine, ethyl p-dimethylaminobenzoateor Michler's ketone. The effect of the amines can be increased by addingaromatic ketones of the benzophenone type. Amines which can be used asoxygen scavengers are, for example, substituted N,N-dialkylanilines, asdescribed in EP-A-339 841. The photopolymerisation can also beaccelerated by adding photosensitisers, which shift or broaden thespectral sensitivity. These are, in particular, aromatic carbonylcompounds, e.g. derivatives of benzophenone, thioxanthone, anthraquinoneor 3-acylcoumarine, and 3-(aroylmethylene)thiazolines, but also eosin,rhodanine and erythrosine dyes.

The compositions according to the invention can also contain aphotoreducible dye, e.g. xanthene, benzoxanthene, benzothioxanthene,thiazine, pyronine, porphyrin or acridine dyes, and/or a trihalomethylcompound which can be cleaved by radiation. Similar compositions aredescribed, for example, in EP-A-445 624.

Further conventional additives are, depending on the application,optical brighteners, fillers, pigments, dyes, wetting agents and flowassistants. Thick and pigmented coatings can be cured by adding glassmicrobeads or powdered glass fibres, as described, for example, in U.S.Pat. No. 5,013,768.

The invention also relates to compositions in which component (a) is atleast one ethylenically unsaturated, photopolymerisable compounddissolved or emulsified in water.

Aqueous radiation-curable prepolymer dispersions of this type arecommercially available in many variants. This is taken to mean adispersion of water and at least one prepolymer dispersed therein. Theconcentration of the water in these systems is, for example, from 5 to80% by weight, in particular from 30 to 60% by weight. Theradiation-curable prepolymer or prepolymer mixture is present, forexample, in a concentration of from 95 to 20% by weight, in particularfrom 70 to 40% by weight. The total of the percentages given for waterand prepolymer in these compositions is in each case 100, and theassistants and additives are additional, in various amounts depending onthe application.

The radiation-curable water-dispersed, frequently also dissolved,film-forming prepolymers are monofunctional or polyfunctionalethylenically unsaturated prepolymers which are known per se for aqueousprepolymer dispersions, can be initiated by free radicals and have, forexample, a content of from 0.01 to 1.0 tool of polymerisable doublebonds per 100 g of prepolymer, and a mean molecular weight of, forexample, at least 400, in particular from 500 to 10,000. Depending onthe application, however, prepolymers having higher molecular weightsare also suitable. For example, polyesters containing polymerisable C--Cdouble bonds and having an acid number of at most 10, polyetherscontaining polymerisable C--C double bonds, hydroxyl-containing productsof the reaction of a polyepoxide containing at least two epoxide groupsper molecule with at least one α,β-ethylenically unsaturated carboxylicacid, polyurethane (meth)acrylates and acrylic copolymers containingα,β-ethylenically unsaturated acrylic radicals, as described in EP-A-12339, are used. It is also possible to use mixtures of these prepolymers.Also suitable are the polymerisable prepolymers described in EP-A-33896, which are thioether adducts of polymerisable prepolymers having amean molecular weight of at least 600, a carboxyl group content of from0.2 to 15% and a content of from 0.01 to 0.8 mol of polymerisable C--Cdouble bonds per 100 g of prepolymer. Other suitable aqueous dispersionsbased on specific alkyl (meth)acrylate polymers are described in EP-A-41125, and suitable water-dispersible, radiation-curable prepolymers madefrom urethane acrylates are disclosed in DE-A-2 936 039.

Further additives which may be present in these aqueousradiation-curable prepolymer dispersions are dispersion aids,emulsifiers, antioxidants, light stabilisers, dyes, pigments, fillers,e.g. talc, gypsum, silica, ruffle, carbon black, zinc oxide, ironoxides, reaction accelerators, flow-control agents, lubricants, wettingagents, thickeners, matting agents, defoamers and other assistants whichare customary in paint technology. Suitable dispersion aids arewater-soluble, high-molecular-weight organic compounds containing polargroups, e.g. polyvinyl alcohols, polyvinylpyrrolidone and celluloseethers. Emulsifiers which can be used are nonionic or possibly ionicemulsifiers.

The photopolymerisable compositions expediently contain thephotoinitiator (b) in an amount of from 0.05 to 15% by weight,preferably from 0.2 to 5% by weight, based on the composition.

In certain cases, it may be advantageous to use mixtures of two or moreof the photoinitiators according to the invention. It is of course alsopossible to use mixtures with known photoinitiators, e.g. mixtures withbenzophenone, acetophenone derivatives, for example α-hydroxycycloalkylphenyl ketones, dialkoxyacetophenones, α-hydroxy- orα-aminoacetophenones, 4-aroyl-1,3-dioxolanes, benzoin alkyl ethers andbenzil ketals, monoacylphosphine oxides, bisacylphosphine oxides andfurther titanocenes. If the photoinitiators according to the inventionare used in hybrid systems, cationic photoinitiators, e.g. aromaticsulfonium or iodonium salts or cyclopentadienylarene iron(II) complexsalts, are used in addition to the free-radical curing agents accordingto the invention.

The photopolymerisable compositions can be used for various purposes,for example as printing inks, varnishes, white paints, e.g. for wood ormetal, coating materials, including for paper, wood, metal or plastic,daylight-curable coating material for building and road marking, forphotographic reproduction processes, for holographic recordingmaterials, for image-recording processes or for the production ofprinting plates which can be developed with organic solvents or inaqueous-alkaline media, for the production of masks for screen printing,as dental filling compositions, adhesives, pressure-sensitive adhesives,laminated resins, etch or permanent resists and solder resist masks forelectronic circuits, for the production of three-dimensional articles bymass curing (UV curing in transparent moulds) or by thestereolithography process, as described, for example, in U.S. Pat. No.4,575,330, for the production of composite materials (e.g. styrenicpolyesters, which may also contain glass fibres and other assistants)and other thick-layer compositions, for coating or sealing electroniccomponents, and as coatings for optical fibres. The compounds accordingto the invention may furthermore be used as initiators for emulsionpolymerisation reactions, as initiators of polymerisation for the fixingof ordered states of liquid-crystalline monomers and oligomers, and forcuring powder coatings.

In paints, mixtures of a prepolymer with polyunsaturated monomers andalso a monounsaturated monomer are frequently used. The prepolymer hereis primarily responsible for the properties of the paint film; byvarying it, the person skilled in the art can modify the properties ofthe cured film. The polyunsaturated monomer functions as crosslinkingagent, which makes the paint film insoluble. The monounsaturated monomerfunctions as reactive thinner, by means of which the viscosity isreduced without the need to use a solvent.

Unsaturated polyester resins are usually used in two-component systemstogether with a monounsaturated monomer, preferably styrene. Inphotoresists, specific one-component systems, e.g. polymaleimides,polychalcones or polyimides, as described in DE-A 2 308 830, arefrequently used.

The photocurable compositions according to the invention are suitable,for example, as coating compositions for substrates of all types, e.g.wood, textiles, paper, ceramic, glass, plastics, such as polyesters,polyethylene terephthalates, polyolefins or cellulose acetate, inparticular in the form of films, and metals, such as Al, Cu, Ni, Fe, Zn,Mg or Co and GaAs, Si or SiO₂, onto which a protective coating or, byimagewise exposure, an image is to be applied.

The substrates can be coated by applying a liquid composition, asolution or suspension to the substrate. The choice of solvent andconcentration depend primarily on the nature of the composition and onthe coating method. The solvent should be inert, i.e. it should notundergo any chemical reaction with the components and it should beremovable again on drying after coating. Examples of suitable solventsare ketones, ethers and esters, such as methyl ethyl ketone, isobutylmethyl ketone, cyclopentanone, cyclohexanone, N-methylpyrrolidone,dioxane, tetrahydrofuran, 2-methoxyethanol, 2-ethoxyethanol,1-methoxy-2-propanol, 1,2-dimethoxyethane, ethyl acetate, n-butylacetate and ethyl 3-ethoxypropionate.

The solution is applied uniformly to a substrate by known coatingmethods, e.g. by spin coating, dip coating, knife coating, curtaincoating, brushing, spraying, in particular by electrostatic spraying,and reverse-roll coating. It is also possible to apply thephotosensitive layer to a temporary, flexible carrier and then to coatthe final substrate, e.g. a copper-laminated circuit board, bytransferring the layer by lamination. The application rate (layerthickness) and the type of substrate (layer carrier) depend on thedesired area of application. The layer thickness range is generally fromabout 0.1 μm to more than 10 μm.

The radiation-sensitive compositions according to the invention are usedas negative resists which have very high photosensitivity and can bedeveloped in aqueous alkaline media without swelling. They are suitableas photoresists for electronics (galvanoresists, etch resists and solderresists), for the production of printing plates, such as offset printingplates or screen printing plates, for chemical milling or asmicroresists in the production of integrated circuits. The possiblelayer carriers and the process conditions of the coated substrates varycorrespondingly.

Films made from polyester, cellulose acetate or resin-coated papers, forexample, are used for photographic image recording; specially treatedaluminium is used for offset printing plates, copper laminates are usedfor the production of printed circuits, and silicone wafers are used forthe production of integrated circuits. Layer thicknesses are generallyfrom about 0.5 to 10 μm for photographic materials and offset printingplates and from 0.4 to about 2 μm for printed circuits.

After the substrates have been coated, the solvent is generally removedby drying, giving a photoresist layer on the carrier.

The term "imagewise" exposure includes both exposure through a photomaskcontaining a predetermined pattern, for example a slide, exposure by alaser beam which is moved, for example, under computer control over thesurface of the coated substrate, generating an image, and exposure tocomputer-controlled electron beams.

After the imagewise exposure of the material and before the development,it may be advantageous to carry out a brief thermal treatment. Only theexposed parts are thermocured. Temperatures used are generally 50°-150°C., preferably 80°-130° C.; the thermal treatment time is generallybetween 0.25 and 10 minutes.

The photocurable composition may furthermore be used in a process forthe production of printing plates or photoresists, as described, forexample, in DE-A-4 013 358. In this process, the composition is exposedbriefly to visible light having a wavelength of at least 400 nm withouta mask before, during or after the imagewise irradiation.

After the exposure and any thermal treatment, the unexposed areas of thephotoresist are removed in a manner known per se using a developer.

The compositions according to the invention, as mentioned above, can bedeveloped in aqueous-alkaline media. Suitable aqueous-alkaline developersolutions are, in particular, aqueous solutions of tetraalkylammoniumhydroxides or alkali metal silicates, phosphates, hydroxides orcarbonates. If necessary, relatively small mounts of wetting agentsand/or organic solvents may be added to the solutions. Typical organicsolvents which can be added in small amounts to the developer liquidsare, for example, cyclohexanone, 2-ethoxyethanol, toluene, acetone andmixtures of these.

Photocuring is of great importance for printing inks, since the dryingtime of the binder is a crucial factor for the rate of production ofgraphic products and should be in the order of fractions of seconds.UV-curable inks are of particular importance for screen printing.

The mixtures according to the invention are, as mentioned above, alsohighly suitable for the production of printing plates. In this case, forexample, mixtures of soluble linear polyamides or styrene-butadiene orstyrene-isoprene rubber, polyacrylates or polymethyl methacrylatescontaining carboxyl groups, polyvinyl alcohols or urethane acrylateswith photopolymerisable monomers, for example acrylamides,methacrylamides, acrylates or methacrylates, and a photoinitiator, areused. Films and plates produced from these systems (wet or dry) areexposed via the negative (or positive) of the print master, and theuncured parts are subsequently eluted with a suitable solvent.

A further area of application of photocuring is in metal coating, forexample in the coating of sheeting and tubes, cans or bottle caps, andthe photocuring of plastic coatings, for example of PVC-based floor orwall coverings.

Examples of the photocuring of paper coatings are the colourlesslacquering of labels, record sleeves or book covers.

Another important use of photocurable compositions is for imagingprocesses aand for the optical production of information carriers. Inthis case, as described above, the layer applied to the carrier (wet ordry) is irradiated through a photomask with UV or visible light, and theunexposed areas of the layer are removed by treatment with a solvent(=developer). The photocurable layer can also be applied to metal byelectrodeposition. The exposed areas are crosslinked/polymeric and thusinsoluble and remain on the carrier. If appropriately stained, visibleimages are formed. If the carrier is a metallised layer, the metal inthe unexposed areas can be removed by etching or increased in thicknessby electroplating after exposing and developing. In this way, printedelectronic circuits and photoresists can be produced.

The photosensitivity of the compositions according to the inventiongenerally extends from the UV range (about 200 nm) to about 600 nm andthus covers a very broad range. Suitable radiation is present, forexample, in sunlight or light from artificial light sources. The lightsources used are therefore a large number of very varying types. Bothpoint sources and large-area lamps (lamp carpets) are suitable. Examplesare: carbon arc lamps, xenon are lamps, mercury medium-pressure,high-pressure and low-pressure lamps, if desired doped with metalhalides (metal halogen lamps), microwave-excited metal vapour lamps,excimer lamps, superactinic fluorescent tubes, fluorescent lamps, argonincandescent lamps, electronic flash lamps, photographic flood lamps,electron beams and X-rays, generated by synchrotrons or laser plasma.The distance between the lamp and the substrate to be coated accordingto the invention can vary, for example between 2 cm and 150 cm,depending on the application and the lamp type and power. Particularlysuitable sources are laser light, e.g. excimer lasers, such as krypton Flasers, for exposure at 248 nm. It is also possible to employ lasers inthe visible range. Here, the high sensitivity of the materials accordingto the invention is very advantageous. This method can be used toproduce printed circuits in the electronics industry, lithographicoffset printing plates or relief printing plates and photographicimage-recording materials.

The invention also relates to the use of the above-described compositionfor the production of paints, printing inks, printing plates, dentalcompositions, resist materials and as an image-recording material, inparticular for holographic recordings.

The invention likewise relates to a coated substrate which has beencoated on at least one surface with a composition as described above,and to a process for the photographic production of relief images, inwhich a coated substrate is exposed imagewise, and the unexposed areasare then removed using a solvent.

The invention therefore .also relates to a process for thephotopolymerisation of nonvolatile, monomeric, oligomeric or polymericcompounds containing at least one ethylenically unsaturated double bond,wherein a compound of the formula I or II is added to the abovementionedcompounds and irradiated with light in the range from 200 to 600 nm.

The examples below illustrate the invention in greater detail. Parts andpercentages, as in the remainder of the description and in the claims,are by weight, unless stated otherwise.

I) Preparation of the Starting Materials

EXAMPLE 1 Preparation of 2,4-dibenzyloxy-6-chloropyrimidine

The reaction is carried out under an argon protective-gas atmosphere.24.8 ml (0.24 mol) of absolute benzyl alcohol in 100 ml of THF are addeddropwise at 25° C. to 9.6 g of NaH (0.24 mol, 60% suspension inparaffin) in 120 ml of tetrahydrofuran (THF). The reaction mixture iswarmed at 50° C. for 0.5 hour, cooled and then added dropwise to asolution, cooled to 0° C., of 13.8 ml of 2,4,6-trichloropyrimidine in100 ml of THF. The mixture is allowed to warm to 25° C. overnight, andis then poured into 200 ml of water. After extraction with toluene threetimes, the combined organic phases are washed with 100 ml of water,dried using MgSO₄, filtered and evaporated on a rotary evaporator.Filtration through silica gel (eluent ethyl acetate:hexane 1:1) gives39.9 g (100% of theory) of the title product.

EXAMPLE 2 Preparation of 2,4-isopropoxy-6-chloropyrimidine

The reaction is carried out under an argon protective-gas atmosphere.4.6 g of sodium in small pieces are refluxed for 4 hours with 180 ml ofisopropanol. The mixture is cooled, giving a light precipitate, which isdissolved in 50 ml of THF. This solution is, after cooling to 0° C.,added dropwise to a solution of 11.5 ml (0.1 mol) of2,4,6-trichloropyrimidine in 20 ml of absolute isopropanol. A whitematerial immediately precipitates. The reaction mixture is allowed towarm to 25° C. overnight. Thin-layer chromatography shows the absence ofstarting material. The solvents are removed on a rotary evaporator andthe residue is taken up in 100 ml of toluene. The resultant suspensionis treated twice with 100 ml of water, and the aqueous phases areextracted a number of times with 100 ml of toluene. The organic phasesare combined and dried using MgSO₄. After filtration, the solvent isremoved, giving 22.8 g of a residue (99.1%). Separation on SiO₂ (eluentdiethyl ether:hexane 5:95) gives 18 g (78.3% of theory) of the puretitle compound.

EXAMPLE 3 Preparation of6-chloro-4-(3-methylbut-1-oxy)-2-phenylpyrimidine

The reaction is carried out under an argon protective-gas atmosphere. Asolution of 6.7 g (60.5 mmol) of sodium t-amylate in 50 ml of3-methylbutanol is added dropwise to a solution, cooled to 0° C., of12.4 g of 4,6-dichloro-2-phenylpyrimidine in 50 ml of 3-methylbutanol.The reaction mixture is allowed to warm to 25° C. overnight. Thin-layerchromatography shows the absence of starting material. The reactionmixture is poured into 180 ml of water and extracted three times with 80ml of ethyl acetate. Combined organic phases are washed with water,dried using MgSO₄ and filtered. Removal of the solvent gives 14.6 g (96%of theory) of the title compound.

Elementary analysis:

    ______________________________________                                        calc.:   C:      69.1%     found: C:    69.1%                                          H:       6.2%            H:     6.4%                                          N:      10.1%            N:    10.0%                                          Cl:     12.8%            Cl:   12.6%                                 ______________________________________                                    

EXAMPLE 4 Preparation of 6-chloro-2,4-diethoxypyrimidine

7.35 g (0.32 mol) of sodium in small pieces are added under an argonprotective-gas atmosphere to 100 ml of absolute ethanol. The suspensionis kept under reflux until the sodium has dissolved The solution iscooled and added dropwise at 0° C. to a solution of 18.4 ml (0.16 mol)of 2,4,6-trichloropyrimidine in 100 ml of ethanol. The temperature isslowly increased to 25° C., the ethanol is removed on a rotaryevaporator, and 100 ml of water are added. The mixture is then extractedthree times with 100 ml of toluene. The combined organic phases arewashed twice with 100 ml of water in each case, dried over MgSO₄,filtered and evaporated, giving 32.5 g of crude product Purification bySiO₂ flash chromatography with hexane as eluent gives 24.9 g (76.9% oftheory).

Elementary analysis:

    ______________________________________                                        calc.:   C:      47.4%     found: C:    48.3%                                          H:       5.5%            H:     5.8%                                          N:      13.8%            N:    13.8%                                          Cl:     17.5%            Cl:   17.0%                                 ______________________________________                                    

EXAMPLES 5-8

The compounds of Examples 5-8 are prepared analogously to compounds ofExample 1 or 3 and are shown in Table 1 below.

                  TABLE 1                                                         ______________________________________                                         ##STR38##                                                                                            Yield  Elemental analysis [%]                         Ex.  R         Synthesis                                                                              [%]    atom/calculated/found                          ______________________________________                                        5    methoxy-  A        48.3   C:    45.7  46.7                                    ethyl                     H:    5.8   5.7                                                               N:    10.7  10.5                               6    3-methyl- C        51.3   C:    58.6  59.7                                    but-1-yl                  H:    8.1   8.3                                                               N:    9.8   9.4                                                               Cl:   12.4  12.2                               7    cyclo-    A        42.8   C:    61.8  61.4                                    hexyl                     H:    7.5   7.6                                                               N:    9.0   8.8                                                               Cl:   11.4  12.7                               8    cyclo-    A        99.9   C:    63.8  64.2                                    hexyl-                    H:    8.0   8.3                                     methyl                    N:    8.3   8.1                                                               Cl:   10.5  10.4                               ______________________________________                                         A: Method of Example 1                                                        C: Method of Example 3                                                   

EXAMPLE 9 Preparation of 2,4-dichloro-6-(3-methylbut-1-oxy)pyrimidine

A solution of 28.6 g (0.26 mol) of sodium tert-amylate in 150 ml of3-methylbutanol is stirred at 45°-50° C. for 30 minutes, cooled to 20°C. and added dropwise at -30° C. to a solution of 30 ml (0.26 mol) oftrichloropyrimidine in 150 ml of 3-methylbutanol. When the solution hasbeen added, the temperature is 0° C. The reaction mixture is left tostand overnight. The solvent is removed and the residue is taken up in150 ml of water. Extraction three times with toluene, drying of thecombined organic phases using MgSO₄ and evaporation give 60.36 g (98.7%of theory) of the title compound.

Elemental analysis:

    ______________________________________                                        calc.:   C:      46.0%     found: C:    45.9%                                          H:       9.1%            H:     9.1%                                          N:      11.9%            N:    12.0%                                          Cl:     30.2%            Cl:   30.6%                                 ______________________________________                                    

EXAMPLE 10 Preparation of6-chloro-2-isobutylthio-4-(3-methylbut-1-oxy)pyrimidine

A solution of 6.7 ml (55.3 mmol) of isobutyl mercaptan in 40 ml of THFis added dropwise to a suspension of 2.2 g of NaH in 90 ml of THF.During this addition, the temperature is prevented from rising above 50°C. by cooling. The solution is cooled to 20° C. and added to a solutionof 13.0 g of 2,4-dichloro-6-(3-methylbut-1-oxy)pyrimidine in 80 ml ofTHF at -10° C. When the temperature has slowly risen to 25° C., thereaction mixture is poured into 200 ml of water. Extraction three timeswith toluene, drying of the combined organic phases using MgSO₄ andevaporation of the solvent give 17.3 g of a mixture. Separation on SiO₂(petroleum ether 80°-110° C.) gives 11.5 g (71.9% of theory) of thetitle product.

Elemental analysis:

    ______________________________________                                        calc.:   C:      54.1%     found: C:    57.2%                                          H:       7.3%            H:     8.0%                                          N:       9.7%            N:     8.8%                                          S:      11.1%            S:    10.4%                                          Cl:     12.3%            Cl:   11.0%                                 ______________________________________                                    

EXAMPLE 11 Preparation of 5-bromo-2,4-di(1,1-dimethylpropoxy)pyrimidine

11.1: 5-Bromouracil

39.4 g (0.35 mol) of uracil are dissolved in 200 ml of acetic acid, andthe mixture is warmed to 70° C. The mixture is added dropwise over thecourse of 2 hours to a solution of 20 ml (0.38 mol) of bromine dissolvedin 200 ml of acetic acid. The orange suspension is held at 70° C.overnight and then cooled to 0°-5° C. The precipitate obtained isfiltered off, washed with 200 ml of cold water and dried, giving 60.2 gof 5-bromouracil (89.7% of theory).

Elemental analysis:

    ______________________________________                                        calc.:   C:      25.16%    found: C:    25.26%                                         H:       1.58%           H:     1.62%                                         N:      14.67%           N:    14.69%                                         Br:     41.84%           Br:   41.66%                                ______________________________________                                    

11.2: 5-Bromo-2,4-dichloropyrimidine ml of dimethylaniline and 40 g(0.21 mol) of 5-bromouracil are added at room temperature to 580 ml (6.3mol) of phosphorus oxychloride, and the mixture is refluxed for 4.5hours. The reaction mixture is slowly poured into ice water andextracted a number of times with dichloromethane. The combined organicphases are dried using MgSO₄, and filtered, and the solvent isevaporated on a rotary evaporator, giving 15 g (31.4% of theory) of5-bromo-2,4-dichloropyrimidine.

Elemental analysis:

    ______________________________________                                        calc.:   C:      21.08%    found: C:    21.09%                                         H:       0.44%           H:     0.48%                                         N:      12.29%           N:    12.39%                                         Cl:     31.12%           Cl:   29.65%                                         Br:     35.07%           Br:   34.75%                                ______________________________________                                    

11.3: 5-Bromo-2,4-di(1,1-dimethylpropyloxy)-pyrimidine

21.5 g (0.195 mol) of sodium t-amylate are dissolved in 150 ml of THFunder an argon protective gas, and 14.8 g (0.065 mol) of5-bromo-2,4-dichloropyrimidine, dissolved in 80 ml of THF, are added.The reddish suspension is refluxed for 4 hours. The cooled reactionmixture is poured into 150 ml of water and extracted three times withtoluene. Drying of the combined organic phases over MgSO₄ and removal ofthe solvent give 20.25 g of crude product. Purification on SiO₂ usingethyl acetate:petroleum ether as eluent in the ratio 5:95 gives 19.25 g(89.5% of theory) of the title compound.

Elemental analysis:

    ______________________________________                                        calc.:   C:      50.8%     found: C:    52.2%                                          H:       7.0%            H:     7.6%                                          N:       8.5%            N:     8.3%                                          Br:     24.1%            Br:   22.8%                                 ______________________________________                                    

EXAMPLE 12 Preparation of5-bromo-2,4,6-tris(3-methylbut-1-oxy)pyrimidine

12.1: 2,4,6-Tris(3-methylbut-1-oxy)pyrimidine

49.5 g (0.45 mol) of sodium t-amylate are dissolved in 200 ml ofisopentanol at 50° C., and 13 ml (0.11 mol) of trichloropyrimidine in 50ml of isopentanol are added dropwise to this solution over the course of30 minutes. After the mixture has been warmed at 50° C. for one hour,thin-layer chromatography shows that the mixture no longer contains anystarting material. The solvent is removed on a rotary evaporator, andthe residue is poured into 200 ml of water. The mixture is extractedthree times with 150 ml of toluene in each case, and the organic phasesare dried using MgSO₄ and filtered. Removal of the solvent gives 37.5 g(98.7% of theory) of 2,4,6-tris(3-methylbut-1-oxy)pyrimidine.

Elemental analysis:

    ______________________________________                                        calc.:   C:      67.4%     found: C:    67.3%                                          H:      10.1%            H:    10.6%                                          N:       8.3%            N:     7.6%                                 ______________________________________                                    

12.2: 5-Bromo-2,4,6-tris(3-methylbut-1-oxy)pyrimydine

35.0 g (0.1 mol) of 2,4,6-tris(3-methylbut-1-oxy)pyrimidine aredissolved in 75.7 ml of acetic acid and 14.7 ml of acetic anhydride, andthe solution is warmed to 100° C. 23 g (0.13 mol) of N-bromosuccinimideare added, and the temperature of the reaction mixture is adjusted to120° C. for 10 minutes and then held at 100° C. for 3 hours. After themixture has been cooled, the solvent is removed on a rotary evaporator,100 ml of water are added, and the suspension is extracted three timeswith 100 ml of dichloromethane. The combined organic phases are washedwith water, dried using MgSO₄ and filtered, and the solvent is removedon a rotary evaporator. Purification by SiO₂ flash chromatography usingspecial boiling point spirit (80°-110° C.) as eluent gives 33.6 g (77.9%of theory) of the title compound as a colourless liquid.

Elemental analysis:

    ______________________________________                                        calc.:   C:      54.7%     found: C:    56.8%                                          H:       8.0%            H:     8.5%                                          N:       6.7%            N:     6.2%                                          Br:     19.1%            Br:   17.7%                                 ______________________________________                                    

EXAMPLE 13 Preparation of 5-bromo-2,4.6-tri(cyclohexyloxy)pyrimidine

20.3 ml (0.1925 mol) of cyclohexanol in 40 ml of THF are added dropwiseunder an argon protective gas to 5.8 g (0.1925 mol) of sodium hydride(60% in oil) in 100 ml of THF. When the addition is complete, thereaction mixture is heated at 50° C. for 40 minutes, and 6.3 ml (0.055mol) of 2,4,6-trifluoropyrirnidine in 40 ml of THF are added dropwisewhile the temperature is held at 50° C. The reaction mixture is cooled,poured into 180 ml of water and extracted three times with toluene. Thecombined organic phases are washed twice with 100 ml of water, driedover MgSO₄ and filtered, and the solvent is removed on a rotaryevaporator. Purification is carried out by medium-pressurechromatography on silica gel LiChroprep Si 60, particle size 25-40 μm,from MERCK, with toluene:hexane 1:1 as eluent.

Elemental analysis:

    ______________________________________                                        calc.:   C:      70.6%     found: C:    71.4%                                          H:       9.2%            H:    10.1%                                          N:       7.5%            N:     6.9%                                 ______________________________________                                    

The bromination step is carried out as described under Example 12.2. Thecompound has a melting range of 120°-124° C.

EXAMPLES 14-18

The compounds of Examples 14-18 are prepared analogously to the compoundof Example 13. In Examples 14 and 17, the THF is replaced bydimethylacetamide (DMA). The bromination step is carried out asdescribed under Example 12.2. The compounds are listed in Table 2 below.

                  TABLE 2                                                         ______________________________________                                         ##STR39##                                                                                     Melting range                                                                             Elemental analysis [%]                           Ex.  R           [°C.]                                                                              Atom/calculated/found                            ______________________________________                                        14   tetrahydro- 120-124     C:    49.7  50.3                                      furfuryl                H:    5.9   6.2                                                               N:    6.1   5.9                                                               Br:   17.4  16.6                                 15   isopropyl   oil         C:    46.8  46.9                                                              H:    6.4   6.3                                                               N:    8.4   8.4                                                               Br:   24.0  24.3                                 16   ethyl       42-44       C:    41.3  41.4                                                              H:    5.2   5.2                                                               N:    9.6   9.6                                                               Br:   27.5  27.2                                 17   methoxyethyl                                                                              oil         C:    41.0  41.4                                                              H:    5.6   5.7                                                               N:    7.4   7.4                                                               Br:   21.0  19.8                                 18   cyclohexyl- 76-81       C:    60.6  61.1                                      methyl                  H:    7.9   8.6                                                               N:    5.7   5.4                                                               Br:   16.1  15.5                                 ______________________________________                                    

EXAMPLE 19 Preparation of 2,4,6-trimethoxypyrimidine

13.5 ml of 2,4,6-trichloropyrimidine in 80 ml of methanol are addeddropwise, with cooling and under an argon protective gas to 106 ml of a5.4M solution of sodium methoxide in methanol (0.576 mol). After themixture has been refluxed for 90 minutes, the solvent is removed and theresidue is poured into water. The mixture is extracted twice withtoluene, the organic phases are dried using MgSO₄ and filtered, and thesolvent is removed. The target product is obtained in quantitativeyield. NMR data: signals at 3.95 ppm (singlet for 9H) and 5.7 ppm(singlet for 1H). The bromination step is carried out as described underExample 12.2. NMR data: signals at 4 ppm (singlet for 9H).

EXAMPLE 20 Preparation of6-chloro-4-(3-methylbut-1-oxy)-2-propylpyrimidine

The compound of Example 20 is prepared analogously to the compound ofExample 3, with the 4,6-dichloro-2-phenylpyrimidine being replaced by4,6-dichloro-2-propylpyrimidine.

Elemental analysis:

    ______________________________________                                        calc.:   C:      59.4%     found: C:    60.2%                                          H:       7.9%            H:     8.2%                                          N:      11.5%            N:    11.3%                                          Cl:     14.6%            Cl:   13.7%                                 ______________________________________                                    

EXAMPLE 21 Preparation of6-chloro-4-(2-ethylhexyloxy)-2-propylpyrimidine

The compound of Example 21 is prepared analogously to the compound ofExample 3, with 4,6-dichloro-2-phenylpyrimidine being replaced by4,6-dichloro-2-propylpyrimidine and 3-methylbutanol by 2-ethylhexanol.

NMR data (in CDCl₃): signals at 6.6 ppm (singlet for 1H), 4.3 ppm(doublet for 2H), 3.8 ppm (doublet of doublets) and 0.7-2.2 ppm(multiplet for 20H).

EXAMPLE 22 Preparation of6-chloro-4-(3-methylbut-1-oxy)-2-i-propylpyrimidine

The compound of Example 22 is prepared analogously to the compound ofExample 3, with 4,6-dichloro-2-phenylpyrimidine being replaced by4,6-dichloro-2-i-propylpyrimidine

NMR data (in CDCl₃): signals at 6.5 ppm (singlet for 1H), 4.4 ppm(doublet for 2H), 3.1 ppm (septet for 1H), 1.0-2.2 ppm (multiplet for2H), 1.3 ppm (doublet for 6H) and 1.0 ppm (doublet for 6H).

EXAMPLE 23 Preparation of6-chloro-4-(2-ethylhexyloxy)-2-i-propylpyrimidine

The compound of Example 23 is prepared analogously to the compound ofExample 3, with 4,6-dichloro-2-phenylpyrimidine being replaced by4,6-dichloro-2-i-propylpyrimidine and 3-methylbutanol by 2-ethylhexanol.

NMR data (in CDCl₃): signals at 6.5 ppm (singlet for 1H), 4.3 ppm(doublet for 2H), 3.1 ppm (septet for 1H) and 0.7-2.1 ppm (multiplet for21H).

EXAMPLE 24 Preparation of6-chloro-4-(3-methylbut-1-oxy)-2-decylpyrimidine

The compound of Example 24 is prepared analogously to the compound ofExample 3, with 4,6-dichloro-2-phenylpyrimidine being replaced by4,6-dichloro-2-decylpyrimidine.

NMR data (in CDCl₃): signals at 6.5 ppm (singlet for 1H), 4.4 ppm(doublet for 2H), 2.8 ppm (triplet for 2H) and 0.7-2.1 ppm (multipletfor 28H).

EXAMPLE 25 Preparation of 6-chloro-4-(2-ethylhexyloxy)-2-decylpyrimidine

The compound of Example 25 is prepared analogously to the compound ofExample 3, with 4,6-dichloro-2-phenylpyrimidine being replaced by4,6-dichloro-2-decylpyrimidine and 3-methylbutanol by 2-ethylhexanol.

NMR data (in CDCl₃): signals at 6.5 ppm (singlet for 1H), 4.3 ppm(doublet for 2H), 2.8 ppm (triplet for 2H) and 0.7-2.0 ppm (multipletfor 34H).

EXAMPLES 26-35

The compounds of Examples 26-35 are prepared analogously to thecompounds of Examples 3, 4 or 43.3 using the respective alcohols oralkoxides. The results are shown in Table 3 below.

                                      TABLE 3                                     __________________________________________________________________________     ##STR40##                                                                               Melting range                                                                          Elemental analysis [%]                                                                    Preparation                                   Ex.                                                                              R       [°C.]                                                                           Atom/calculated/found                                                                     method                                        __________________________________________________________________________    26 methyl  66-71    C:  62.3                                                                              62.1                                                                              D                                                                 H:  4.2 4.5                                                                   N:  9.1 8.6                                                                   Cl: 11.5                                                                              11.0                                              27 ethyl   52-69    C:  63.3                                                                              63.2                                                                              Z                                                                 H:  4.7 4.6                                                                   N:  8.7 8.3                                                                   Cl: 11.0                                                                              11.0                                              28 i-propyl                                                                              57-64    C:  62.8                                                                              62.8                                                                              C                                                                 H:  5.3 5.3                                                                   N:  11.3                                                                              11.1                                                                  Cl: 14.3                                                                              14.2                                              29 i-butyl brown    C:  64.0                                                                              64.3                                                                              C                                                        liquid   H:  5.8 5.9                                                                   N:  10.7                                                                              10.5                                                                  Cl: 13.5                                                                              13.2                                              30 decyl   40-45    C:  69.3                                                                              67.2                                                                              C                                                                 H:  7.9 7.2                                                                   N:  8.1 8.5                                                                   Cl: 10.2                                                                              13.0                                              31 2-ethyl-                                                                              yellow   C:  68.1                                                                              67.8                                                                              C                                                hexyl   oil      H:  6.9 7.3                                                                   N:  8.8 8.7                                               32 cyclohexyl                                                                            44-48    C:  66.6                                                                              66.7                                                                              Z                                                                 H:  5.9 6.1                                                                   N:  9.7 8.9                                                                   Cl: 12.3                                                                              11.5                                              33 cyclohexyl-                                                                           55-63    C:  67.4                                                                              66.4                                                                              Z                                                methyl           H:  6.3 6.1                                                                   N:  9.3 9.3                                                                   Cl: 11.7                                                                              13.1                                              34 methoxyethyl                                                                          43-46    +)          C                                             35 phenoxyethyl                                                                          123-127  C:  66.2                                                                              66.0                                                                              Z                                                                 H:  4.6 4.8                                                                   N:  8.6 8.5                                                                   Cl: 10.8                                                                              11.1                                              __________________________________________________________________________     D: Preparation analogous to Example 4                                         C: Preparation analogous to Example 3                                         Z: Preparation analogous to Example 43.3                                      +): NMR data (CDCl.sub.3): signals at 8.3 ppm (multiplet for 2H), 7.4 ppm     (multiplet for 3H), 6.6 ppm (singlet for 1H), 4.6 ppm (multiplet for 2H),     3.7 ppm (multiplet for 2H) and 3.4 ppm (singlet for 3H).                 

EXAMPLE 36 Preparation of6-chloro-2-p-chlorophenyl-4-(2-ethylhexyloxy)pyrimidine

36.1 p-Chlorobenzamidine hydrochloride

(cf. F. C. Schaefer und A. P. Krapcho, Journal of the Chemical Society,Vol. 27, (1962), 1255)

275.14 g (2 mol) of 4-chlorobenzonitrile, 427.9 g of ammonium chloride(8 mol) and 681.2 g (40 mol) of ammonia are introduced into a 6.3 lautoclave. Pressure rises to about 10 bar. The mixture is heated at 125°C. for 18 hours, during which the pressure rises to 65 bar. The solidresidue is dissolved in 2 l of hot water and filtered while warm, thewater phase is rendered basic by means of 30% NaOH. The resultantsuspension is filtered, giving 240.8 g (63.1% of theory) of the product,having a melting point of 158.4°-158.5° C.

Elemental analysis:

    ______________________________________                                        calc.:   C:      54.4%     found: C:    54.2%                                          H:       4.6%            H:     4.6%                                          N:      18.1%            N:    17.7%                                          Cl:     22.9%            Cl:   22.9%                                 ______________________________________                                    

36.2: 2-p-Chlorophenylhydroxypyrimidone

500 ml of methanol and 280.9 g (1.56 mol) of a 30% solution of sodiummethoxide in methanol are mixed in a 2.5 l sulfonation flask under aprotective-gas atmosphere. 120.4 g (0.78 mol) of p-chlorobenzamidinehydrochloride are added, and the mixture is refluxed for 30 minutes.89.4 ml (103.05 g, 0.78 mol) of dimethyl malonate are then addeddropwise over a period of 1.5 hours. The reaction mixture is allowed toreact for a further hour and is then cooled, and the solvent is removedon a rotary evaporator. The residue is suspended in 2 l of water andacidified to a pH of 3-4 using acetic acid. The suspension is filtered,and the filter cake is washed with water and then dried, giving 169.4 g(97.6% of theory) of the product, with a melting point of above 250° C.

Elemental analysis:

    ______________________________________                                        calc.:   C:      54.0%     found: C:    53.4%                                          H:       3.2%            H:     3.3%                                          N:      12.6%            N:    12.2%                                          Cl:     15.9%            Cl:   15.8%                                 ______________________________________                                    

36.3: 2-p-Chlorophenyl-4,6-dichloropyrimidine

90 g (0.4 mol) of 2-p-chlorophenylhydroxypyrimidone and 1 l ofchlorobenzene are warmed to 50° C. in a 2.5 l sulfonation flask under aprotective-gas atmosphere. 219.7 ml of phosphorus oxychloride (2.4 mol)are added dropwise over the course of about 3 hours at such a rate thatthe temperature remains at 50° C. 256 ml (1.6 mol) of dimethylanilineare then added dropwise over the course of about 1 hour, during whichthe temperature is again held at 50° C. The mixture is then warmed at130° C. for about 16 hours and cooled, 2 l of ice water are added, thephases are separated and the aqueous phase is extracted withchlorobenzene. The combined organic phases are dried over MgSO₄,filtered and evaporated on a rotary evaporator. The residue isrecrystallized from methanol, giving 42.8 g (51.5% of theory) of theproduct, having a melting point of 124.0°-124.1° C.

Elemental analysis:

    ______________________________________                                        calc.:   C:      46.3%     found: C:    46.3%                                          H:       1.9%            H:     2.1%                                          N:      10.8%            N:    10.6%                                          Cl:     41.0%            Cl:   40.3%                                 ______________________________________                                    

36.4: 6-Chloro-2-(p-chlorophenyl)-4-(2-ethylhexyloxy)pyrimidine

The conversion of 2-(p-chlorophenyl)-4,6-dichloropyrimidine to6-chloro-2-(p-chlorophenyl)-4-(2-ethylhexyloxy)pyrimidine is carried outanalogously to the method described in Example 3, with4,6-dichloro-2-phenylpyrimidine being replaced by4,6-dichloro-2-(p-chlorophenyl)pyrimidine and 3-methylbutanol by2-ethylhexanol.

Elemental analysis:

    ______________________________________                                        calc.:   C:      61.2%     found: C:    62.7%                                          H:       6.3%            H:     6.7%                                          N:       7.9%            N:     7.2%                                          Cl:     20.1%            Cl:   18.9%                                 ______________________________________                                    

EXAMPLE 37 Preparation of6-chloro-2-(p-chlorophenyl)-4-phenoxyethoxypyrimidine

The compound of Example 37 is prepared analogously to the compound ofExample 36, but the reaction of the 4,6-dichloro starting material isnot carried out by the method of Example 3, but instead by the method ofExample 43.3.

EXAMPLE 38 Preparation of4-chloro-6-(3-methylbut-1-oxy)-2-(p-octylphenylthio)pyrimidine

38.1: p-Octylthiobenzonitrile

103.2 g (0.75 mol) of p-chlorobenzonitrile, 140 g of potassium carbonateand 143.2 ml (0.825 mol) of octanethiol in dimethylacetamide are stirredat 100° C. for about 16 hours in a sulfonation flask under aprotective-gas atmosphere. The white suspension obtained is cooled,poured into ice water and extracted a number of times withdichloromethane. The organic phases are combined, washed with water,dried over MgSO₄, filtered and evaporated, giving 193.1 g of crudeproduct, which is distilled at 92° C./0.1 mm Hg.

38.2: 2-(p-Octylphenylthio)hydroxypyrimidone (without isolation of theamidine intermediate)

100 g (0.404 mol) of 4-octylthiobenzonitrile are dissolved in 300 ml ofxylene in a 2.5 l sulfonation flask, and 41 g (0.525 mol) of a 50%suspension of sodium amide in toluene are added. The suspension isheated to 135° C. After 3.5 hours, the starting materials have reactedfully (check: thin-layer chromatography). The reaction mixture is cooledto 60° C., and 200 ml of methanol are slowly added dropwise. 46.3 ml(0.404 mol) of dimethyl malonate in 100 ml of methanol are addeddropwise to the beige mixture at 60° C. over the course of one hour. Thesuspension, which is difficult to stir, is diluted with 200 ml ofmethanol and left to stand at room temperature for about 16 hours. ThepH is then adjusted to 3 using acetic acid, and the viscous mixture isfiltered. The solid residue is washed with water and dried at 40° C.,giving 68.5 % of theory of the product having a melting point of >250°C.

Elemental analysis:

    ______________________________________                                        calc.:   C:      65.0%     found: C:    64.7%                                          H:       7.3%            H:     7.1%                                          N:       8.4%            N:     8.0%                                          S:       9.6%            S:     9.6%                                 ______________________________________                                    

38.3: 4,6-Dichloro-2-(p-octylphenylthio)pyrimidine

4,6-Dichloro-2-(p-octylphenylthio)pyrimidine is obtained analogously tothe compound of Example 36.3 in a yield of 97.1% from2-(p-octylphenylthio)hydroxypyrimidone.

Elemental analysis:

    ______________________________________                                        calc.:   C:      58.5%     found: C:    58.6%                                          H:       6.0%            H:     6.1%                                          N:       7.6%            N:     7.7%                                          S:       8.7%            S:     9.0%                                          Cl:     19.2%            Cl:   18.0%                                 ______________________________________                                    

38.4: 4-Chloro-6-(3-methylbut-1-oxy)-2-(p-octylphenylthio)pyrimidine

The title product is obtained by the preparation method of Example 3from 4,6-dichloro-2-(p-octylphenylthio)pyrimidine.

Elemental analysis:

    ______________________________________                                        calc.:   C:      65.6%     found: C:    65.8%                                          H:       7.9%            H:     8.0%                                          N:       6.7%            N:     6.6%                                          S:       7.6%            S:     7.7%                                          Cl:      8.4%            Cl:    8.4%                                 ______________________________________                                    

EXAMPLES 39 and 40

The compounds of Examples 39 and 40 are obtained analogously to thepreparation methods shown in Table 4 below from4,6-dichloro-2-(p-octylphenylthio)pyrimidine.

                  TABLE 4                                                         ______________________________________                                         ##STR41##                                                                                         Elemental analysis [%]                                   Example   R          Atom/calc./found                                         ______________________________________                                        39        ethyl      C:       63.4  62.8                                                           H:       7.2   7.2                                                            N:       7.4   7.3                                                            S:       8.5   8.6                                                            Cl:      9.4   9.4                                       40        phenoxy-   C:       66.3  66.1                                                ethyl      H:       6.6   6.6                                                            N:       6.0   5.8                                                            S:       6.8   6.8                                                            Cl:      7.5   6.7                                       ______________________________________                                    

EXAMPLE 41 2-Butoxyphenyl-4-chloro-6-(3-methylbut-1-oxy)pyrimidine

41.1: p-Butoxybenzonitrile

250 ml of butanol and 15.2 g (0.66 mol) of sodium are heated in asulfonation flask under a protective-gas atmosphere until the metal hasfully reacted. The mixture is cooled, p-chlorobenzonitrile is added inportions, and the reaction mixture is subsequently refluxed for about 16hours. The cooled mixture is poured into water and extracted with ethylacetate. The organic phase is then dried using MgSO₄ and filtered, andthe solvent is evaporated, giving 95% of theory of the title product.

Elemental analysis:

    ______________________________________                                        calc.:   C:      75.4%     found: C:    75.4%                                          H:       7.4%            H:     7.5%                                          N:       8.8%            N:     8.1%                                 ______________________________________                                    

41.2: 2-(p-Butoxyphenyl)hydroxypyrimidone

The title product is obtained analogously to the compound of Example38.2 in a yield of 83.3% of theory from p-butoxybenzonitrile. Theproduct melts at 259°-265° C.

Elemental analysis:

    ______________________________________                                        calc.:   C:      64.6%     found: C:    64.5%                                          H:       6.2%            H:     6.2%                                          N:      10.8%            N:    10.6%                                 ______________________________________                                    

41.3 2-(p-Butoxyphenyl)-4,6-dichloropyrimidine

The title product is obtained analogously to the compound of Example38.3 in a yield of 46% of theory from2-(p-butoxyphenyl)hydroxypyrimidone. The product melts at 54°-58° C.

Elemental analysis:

    ______________________________________                                        calc.:   C:     56.6%     found:  C:   56.6%                                           H:      4.8%             H:    4.9%                                           N:      9.4%             N:    9.4%                                           Cl:    23.9%             Cl:  23.8%                                  ______________________________________                                    

41.4: 2-Butoxyphenyl-4-chloro-6-(3-methylbut-1-oxy)pyrimidine

The preparation of2-butoxyphenyl-4-chloro-6-(3-methylbut-1-oxy)pyrimidine is carried outby the method of Example 3 from2-(p-butoxyphenyl)-4,6-dichloropyrimidine. The product is obtained in ayield of 87% of theory and has a melting range of 47°-50° C.

Elemental analysis:

    ______________________________________                                        calc.:   C:     65.4%     found:  C:   65.6%                                           H:      7.2%             H:    7.3%                                           N:      8.0%             N:    7.7%                                           Cl:    10.2%             Cl:   9.9%                                  ______________________________________                                    

EXAMPLE 42 Preparation of2-butoxyphenyl-4-chloro-6-(2-ethylhexyloxy)pyrimidine

The preparation is carried out by the method of Example 43.3 from2-(p-butoxyphenyl)-4,6-dichloropyrimidine. The product is obtained in ayield of 96.8% of theory.

Elemental analysis:

    ______________________________________                                        calc.:   C:     67.6%     found:  C:   67.5%                                           H:      8.0%             H:    7.9%                                           N:      7.2%             N:    7.3%                                           Cl:     9.1%             Cl:   9.4%                                  ______________________________________                                    

EXAMPLE 43 Preparation of4-chloro-2-(p-methylphenylthio)-6-phenoxyethoxypyrimidine

43.1: 2-(p-Methylphenylthio)hydroxypyrimidone

The title compound is obtained by reacting 6-(methylthio)benzonitrilewith sodium amide giving the corresponding amide and reacting thelatter, without prior isolation, with dimethyl malonate by the methoddescribed in Example 38.2. The product, having a melting point of >250°C., is obtained in a yield of 63.3% of theory.

Elemental analysis:

    ______________________________________                                        calc.:   C:     56.4%     found:  C:   55.5%                                           H:      4.3%             H:    4.4%                                           N:     12.0%             N:   11.5%                                           Cl:    13.7%             Cl:  13.2%                                  ______________________________________                                    

43.2: 4,6-Dichloro-2-(p-methylphenylthio)pyrimidine

The title compound is obtained by reacting the pyrimidone describedunder 43.1 by the method described under 38.3. The yield is 74.2% oftheory, and the melting point, after recrystallisation, is 111.6°-113.4°C.

Elemental analysis:

    ______________________________________                                        calc.:   C:     48.7%     found:  C:   48.7%                                           H:      3.0%             H:    3.1%                                           N:     10.3%             N:   10.6%                                           S:     11.8%             S:   12.0%                                           Cl:    26.2%             Cl:  25.8%                                  ______________________________________                                    

43.3: 4-Chloro-2-(p-methylphenylthio)-6-phenoxyethoxypyrimidine 150 mlof 2-methyl-2-butanol, 2.33 g (0.101 mol) of sodium, 13 ml of2-phenoxyethanol and a trace of iron(III) chloride are refluxed in asulfonation flask. The suspension is refluxed until the sodium has fullyreacted. This mixture is cooled, transferred into a dropping funnelunder argon, and added dropwise at 0° C. over the course of 1.5 hours toa mixture of 25 g of 4,6-dichloro-2-(p-methylphenylthio)pyrimidine in150 ml of absolute tetrahydrofuran. The reaction mixture is left to warmto 20° C. over the course of about 16 hours. The mixture is then pouredinto ice water and extracted a number of times with toluene. The organicphases are combined, washed with water, dried over MgSO₄, filtered andevaporated, giving 65% of theory of the title product having a meltingrange of 128°-132° C.

Elemental analysis:

    ______________________________________                                        calc.:   C:     61.2%     found:  C:   61.0%                                           H:      4.6%             H:    4.6%                                           N:      7.5%             N:    7.4%                                           S:      8.6%             S:    8.7%                                           Cl:     9.5%             Cl:   9.8%                                  ______________________________________                                    

EXAMPLE 44 Preparation of4-chloro-6-ethoxy-2-(p-methylphenylthio)pyrimidine

The preparation is carried out analogously to the method described inExample 4; with 2,4,6-trichloropyrimidine being replaced by4,6-dichloro-2-(p-methylphenylthio)pyrimidine. The title compound isobtained in a yield of 82% of theory and in a melting range of 94°-97°C.

Elemental analysis:

    ______________________________________                                        calc.:   C:     55.6%     found:  C:   55.7%                                           H:      4.7%             H:    4.7%                                           N:     10.0%             N:    9.8%                                           S:     11.4%             S:   11.4%                                           Cl:    12.6%             Cl:  12.6%                                  ______________________________________                                    

EXAMPLE 45 Preparation of4-chloro-2-(p-methylphenylthio)-6-(3-methylbut-1-oxy)pyrimidine

The preparation is carried out analogously to the method described inExample 3, with 4,6-dichloro-2-phenylpyrimidine being replaced by4,6-dichloro-2-(p-methylphenylthio)pyrimidine. The title compound isobtained in a yield of 92.4% of theory and in a melting range of 83°-86°C.

NMR data (CDCl₃): signals at 8.3 ppm, 8.16 ppm, 7.3 ppm, 7.16 ppm(AA'BB' system 4H), 6.5 ppm (singlet, 1H), 4.5 ppm (triplet, 2H), 2.5ppm (singlet, 3H), 1.7 ppm (triplet, 2H), 0.9 ppm (doublet, 6H).

EXAMPLE 46 Preparation of4-chloro-2-(p-methylphenylthio)-6-(2-ethylhexyloxy)pyrimidine

The preparation is carried out analogously to the method described inExample 3, with 4,6-dichloro-2-phenylpyrimidine being replaced by4,6-dichloro-2-(p-methylphenylthio)pyrimidine and 3-methylbutanol by2-ethylhexanol. The title compound is obtained as a resin in a yield of85% of theory.

NMR data (CDCl₃): signals at 8.3 ppm, 8.1 ppm, 7.2 ppm, 7.1 ppm (AA'BB'system 4H), 6.5 ppm (singlet, 1H), 4.4 ppm (triplet, 2H), 2.5 ppm(singlet, 3H), 0.8-2.0 ppm (multiplet, 15H).

EXAMPLE 47 Preparation of2-(biphenyl)-4-chloro-6-(3-methylbut-1-oxy)pyrimidine

47.1: 2-(Biphenyl)hydroxypyrimidone

The preparation of the rifle compound is carried out analogously to themethod described in Example 38.2, with the p-chlorobenzonitrile beingreplaced by p-phenylbenzonitrile. The product is obtained in a yield of62% of theory, with a melting point of >250° C.

Elemental analysis:

    ______________________________________                                        calc.:   C:     72.2%     found:  C:   71.6%                                           H:      4.6%             H:    4.6%                                           N:     10.6%             N:   10.0%                                  ______________________________________                                    

47.2: 2-(Biphenyl)-4,6-dichloropyrimidine

The preparation of the rifle compound is carried out analogously to themethod described in Example 38.3. The product is obtained in a yield of62% of theory, with a melting point of 115.0°-115.4° C.

Elemental analysis:

    ______________________________________                                        calc.:   C:     63.8%     found:  C:   63.9%                                           H:      3.3%             H:    3.6%                                           N:      9.3%             N:    8.8%                                           Cl:    23.5%             Cl:  22.6%                                  ______________________________________                                    

47.3 2-(Biphenyl)-4-chloro-6-(3-methylbut-1-oxy)pyrimidine

The preparation method and physical data of the title compound are shownin Table 5.

EXAMPLES 48 and 49:

The compounds of Example 48 and 49 and their physical data are shown inTable 5 below.

                                      TABLE 5                                     __________________________________________________________________________     ##STR42##                                                                    Ex-        Melting    Yield                                                                             Elemental analysis [%]                              ample                                                                              R     range [°C.]                                                                  Synthesis                                                                          [%] Atom/cacl./found                                    __________________________________________________________________________    47.3 3-methyl-                                                                           53-57 Z    57  C:  71.5                                                                              71.5                                             but-1-yl             H:  6.0 6.0                                                                   N:  7.9 7.7                                                                   Cl  10.1                                                                              9.8                                         48   2-ethyl-                                                                            resin A    80.3                                                                              C:  72.8                                                                              72.8                                             hexyl                H:  7.1 6.8                                                                   N:  7.1 6.8                                                                   Cl: 9.0 9.2                                         49   phenoxy-                                                                            123-127                                                                             Z    72  C:  71.6                                                                              71.3                                             ethyl                H:  4.8 4.7                                                                   N:  7.0 6.9                                                                   Cl: 8.8 8.3                                         __________________________________________________________________________     A: Preparation analogous to Example 1                                         Z: Preparation analogous to Example 43.3                                 

EXAMPLE 50 Preparation of4-chloro-2-(p-phenylphenylthio)-6-(3-methylbut-1-oxy)pyrimidine

50.1: 2-(Phenylthiophenyl)benzonitrile

The compound is prepared analogously to the method described in Example38.1. The title compound obtained has a melting range of 110°-115° C.

50.2: 2-(Phenylthiophenyl)hydroxypyrimidone

The title compound is prepared analogously to the compound of Example38.2. It is obtained in a yield of 63.8% of theory, with a melting pointabove 250° C.

Elemental analysis:

    ______________________________________                                        calc.:   C:     64.9%     found:  C:   64.5%                                           H:      4.1%             H:    4.2%                                           N:      9.5%             N:    9.2%                                           S:     10.8%             S:   10.8%                                  ______________________________________                                    

50.3: 4,6-Dichloro-2-(p-phenylthiophenyl)pyrimidine

The title compound is prepared analogously to the compound of Example38.3. It is obtained in a yield of 91.9% of theory, with a melting rangeof 94°-97° C.

Elemental analysis:

    ______________________________________                                        calc.:   C:     57.7%     found:  C:   58.5%                                           H:      3.0%             H:    3.3%                                           N:      8.4%             N:    8.4%                                           S:      9.6%             S:    9.6%                                           Cl:    21.3%             Cl:  19.2%                                  ______________________________________                                    

50.4: 4-Chloro-2-(p-phenylthiophenyl)-6-(3-methylbut-1-oxy)pyrimidine

The compound of Example 50.4 and the preparation method and physicaldata thereof are shown in Table 6.

EXAMPLES 51 and 52:

The starting materials for the compounds of Examples 51 and 52 areprepared analogously to the compounds of Examples 38.1-38.3. Thereaction to give the final product is carried out by the method shown inTable 6 below.

                  TABLE 6                                                         ______________________________________                                         ##STR43##                                                                                   Melting              Elemental                                 Ex-            range    Yield Syn-  analysis [%]                              ample R        [°C.]                                                                           [%]   thesis                                                                              Atom/calc./found                          ______________________________________                                        50.4  3-methyl-                                                                              47-51    42    Z     C:   65.5 65.3                                  but-1-yl                      H:   5.5  5.4                                                                 N:   7.3  7.3                                                                 S:   8.3  8.5                                                                 Cl:  9.2  9.1                             51    2-ethyl- viscous  80    Z     C:   67.5 68.5                                  hexyl    liquid               H:   6.4  6.8                                                                 N:   6.6  6.1                                                                 S:   7.5  7.2                                                                 Cl:  8.3  7.5                             52    phenoxy- 101-105  54    Z     C:   66.3 66.2                                  ethyl                         H:   4.4  4.5                                                                 N:   6.4  6.3                                                                 S:   7.4  7.5                                                                 Cl:  8.2  7.7                             ______________________________________                                         Z: Preparation method analogous to Example 43.3                          

EXAMPLE 53 Preparation of4-chloro-2-(p-dimethylaminophenyl)-6-(3-methylbut-1-oxy)pyrimidine

53.1: 2-(p-Dimethylaminophenyl)hydroxypyrimidinone

The title product is prepared analogously to the compound of Example38.2 and in a yield of 84.1% of theory, with a melting point of above250° C.

Elemental analysis:

    ______________________________________                                        calc.:   C:     62.3%     found:  C:   56.9%                                           H:      5.7%             H:    6.1%                                           N:     18.2%             N:   16.4%                                  ______________________________________                                    

53.2 2-(p-Dimethylaminophenyl)4,6-dichloropyrimidine

The compound is prepared analogously to the compound of Example 38.3. Itis obtained in a yield of 63.8% of theory, with a melting range of168.5°-169.5° C.

Elemental analysis:

    ______________________________________                                        calc.:   C:     53.8%     found:  C:   54.6%                                           H:      4.1%             H:    4.3%                                           N:     15.7%             N:   15.7%                                           Cl:    26.4%             Cl:  25.2%                                  ______________________________________                                    

53.3: 4-Chloro-2-(p-dimethylaminophenyl)-6-(3-methylbut-1-oxy)pyrimidine

The title product is prepared by the method of Example 43.3. It isobtained in a yield of 75.3% of theory, with a melting range of 83°-93°C.

Elemental analysis:

    ______________________________________                                        calc.:   C:     63.8%     found:  C:   63.7%                                           H:      6.9%             H:    6.8%                                           N:     13.1%             N:   13.3%                                           Cl:    11.1%             Cl:  11.1%                                  ______________________________________                                    

EXAMPLE 54 Preparation of4-chloro-2-pyrrolo-6-(3-methylbut-1-oxy)pyrimidine

54.1: 4,6-Dichloro-2-pyrrolopyrimidine

19.7 g (0.12 mol) of 2-amino-4,6-dichloropyrimidine, 37 g (0.24 mol) ofdimethoxytetrahydrofuran and 0.05 g of p-toluenesulfonic acid are heatedto 140° C., and the methanol formed is immediately removed bydistillation. The mixture is then stirred at 140° C. for 2 hours,cooled, diluted with dichloromethane and filtered through SiO₂, thesolvent is removed, and the product is purified by column chromatographywith hexane as eluent, giving 16.3 g, i.e. 63.2% of theory. Afterrecrystallisation from methanol, the product has a melting point of53.3°-56.3° C.

54.2: 4-Chloro-2-pyrrolo-6-(3-methylbut-1-oxy)pyrimidine

4-Chloro-2-pyrrolo-6-(3-methylbut-1-oxy)pyrimidine is preparedanalogously to the method of Example 3 from4,6-dichloro-2-pyrrolopyrimidine.

NMR data (CDCl₃): signals at 7.6 ppm (triplet, 2H),6.4 ppm (singlet,1H), 6.2 ppm (triplet, 2H), 4.4 ppm (triplet, 2H), 1.7 ppm (triplet, 3H)and 1.0 ppm (doublet, 6H).

EXAMPLE 55 Preparation of 4,6-di(3-methylbut-1-oxy)-2-phenylpyrimidine

The preparation is carried out analogously to the method described inExample 12.1, with the trichloropyrimidine being replaced by4,6-dichloro-2-phenylpyrimidine. A yellow liquid is obtained in a yieldof 89.3% of theory.

Elemental analysis:

    ______________________________________                                        calc.:   C:     73.1%     found:  C:   73.1%                                           H:      8.6%             H:    8.6%                                           N:      8.5%             N:    8.6%                                  ______________________________________                                    

EXAMPLE 56 Preparation of5-bromo-4,6-di(3-methylbut-1-oxy)-2-phenylpyrimidine

The title product is obtained as a colourless liquid analogously to themethod described in Example 12.2 in a yield of 72.4% of theory.

Elemental analysis:

    ______________________________________                                        calc.:  C:      59.0%     found:  C:    59.4%                                         H:       6.7%             H:     6.7%                                         N:       6.9%             N:     6.8%                                         Br:     19.6%             Br:   19.3%                                 ______________________________________                                    

EXAMPLE 57 Preparation of 6-chloro-4-(2-ethylhexyl) pyrimidine

The compound is prepared analogously to the method described in Example3, with 4,6-dichloro-2-phenylpyrimidine being replaced by4,6-dichloropyrimidine and 3-methylbutanol by 2-ethylhexanol. Yield:76.2% of theory.

NMR data (CDCl₃): signals at 8.4 ppm (singlet, 1H), 6.7 ppm (singlet,1H), 4.4 ppm (doublet, 2H) and 0.8-2.0 ppm (multiplet, 15H).

II) Preparation of the Titanocenes

EXAMPLE 58 Preparation ofbis[cyclopentadienyl]bis[6-chloro-2,4-di(3-methylbut-1-oxy)pyrimidinyl]titanium

5.7 g (19.8 mmol) of 6-chloro-2,4-di(3-methylbut-1-oxy)pyrimidine in 40ml of absolute tetrahydrofuran (THF) are cooled to -40° C. in a flaskfitted with magnetic stirrer and argon inlet. 12.4 ml (19.8 mmol) of a1.6M solution of n-butyllithium in hexane are added dropwise to thissolution with stirring. 2.25 g (9 mmol) of soliddicyclopentadienyltitanium dichloride are added to the resultant orangesolution at -40° C. The resultant suspension is allowed to warm slowlyto 25° C. The mixture is then poured into 40 ml of water and filteredthrough ®Hyflo. The aqueous phase is separated off, and the red organicphase is dried using magnesium sulfate, filtered and evaporated on arotary evaporator. The residue is purified by flash chromatography (SiO₂; eluent: ethyl acetate/special boiling point spirit [80°-110° C.]5:95), giving 2.7 g (40% yield) of the title compound having a meltingrange of 89°-96° C.

Elemental analysis:

    ______________________________________                                        calc.:   C:     60.9%     found:  C:   60.0%                                           H:      7.3%             H:    7.4%                                           N:      7.5%             N:    6.9%                                           Cl:     9.5%             Cl:   9.4%                                  ______________________________________                                    

EXAMPLES 59-65

The compounds of Examples 60-66 are prepared analogously to the compoundof Example 58. Their structures and physical data are shown in Table 7below.

                  TABLE 7                                                         ______________________________________                                         ##STR44##                                                                                   Melting   Yield Elemental analysis [%]                         Ex.  R         range [°C.]                                                                      [%]   Atom/calculated/found                          ______________________________________                                        59   methyl    175-178   --    --                                             60   ethyl     140-150   55.2  C:    53.7 53.8                                                               H:    5.5  5.0                                                                N:    9.6  9.5                                                                Cl:   12.2 12.0                                61   iso-      170-175   38.2  C:    56.5 56.6                                     propyl                    H:    6.0  5.8                                                                N:    8.8  8.1                                                                Cl:   11.1 10.5                                62   methoxy-  --        28.6  C:    51.4 50.9                                     ethyl                     H:    5.5  5.5                                                                N:    8.0  8.2                                                                Cl:   10.1 10.2                                63   cyclo-    89-96     13.9  C:    63.2 63.4                                     hexyl*                    H:    6.8  7.1                                                                N:    7.0  6.6                                                                Cl:   8.9  8.9                                 64   cyclo-    164-172   49.0  C:    64.7 65.3                                     hexyl-                    H:    7.3  7.9                                      methyl                    N:    6.6  6.5                                                                Cl:   8.3  7.8                                 65   benzyl    168-175   30.6  C:    66.6 65.9                                                               H:    4.6  4.9                                                                N:    6.8  6.1                                                                Cl:   8.6  7.7                                 ______________________________________                                         *The flash chromatography was carried out using ethyl acetate:hexane 20:8     as eluent                                                                

EXAMPLES 66 and 67

The compounds of Examples 66 and 67 are prepared analogously to thecompound of Example 58, with the dicyclopentadienyltitanium dichloridebeing replaced by bis(methylcyclopentadienyl)titanium dichloride. Thestructures and physical data of the compounds are shown in Table 8.

                  TABLE 8                                                         ______________________________________                                         ##STR45##                                                                                  Melting   Yield  Elemental analysis [%]                         Ex.  R        range [°C.]                                                                      [%]    Atom/calculated/found                          ______________________________________                                        66   methyl   169-173   --     C:    55.2 55.5                                                               H:    5.6  6.1                                                                N:    9.2  8.4                                 67   ethyl    115-123   11     C:    57.4 56.4                                                               H:    5.9  6.0                                                                N:    10.3 10.1                                ______________________________________                                    

EXAMPLE 68 Preparation ofChlorobis(cyclopentadienyl)(6-chloro-2,4-dicyclohexyloxypyrimidinyl)titanium

6.15 g (19.8 mmol) of 6-chloro-2,4-bis(cyclohexyloxy)pyrimidine aredissolved in 40 ml of THF under argon as protective gas, the solution iscooled to -40° C., and 12.4 ml of n-butyllithium (1.6M/hexane) are addeddropwise. 2.25 g (9 mmol) of solid biscyclopentadienyltitaniumdichloride are added to the resultant solution at -40° C. The reactionmixture is allowed to warm slowly from -40° C. to 25° C., is then pouredinto 40 ml of water and is filtered through ®Hyflo. The aqueous phase isseparated off, and the organic phase is dried using magnesium sulfate,filtered and evaporated on a rotary evaporator. The residue is separatedby flash chromatography (SiO₂), giving 1.0 g of the compound fromExample 63 and 0.9 g of the title compound, having a melting range of145°-155 ° C.

Elemental analysis:

    ______________________________________                                        calc.:   C:     59.7%     found:  C:   60.3%                                           H:      6.2%             H:    6.2%                                           N:      5.4%             N:    6.9%                                           Cl:    13.6%             Cl:  13.1%                                  ______________________________________                                    

EXAMPLE 69 Preparation ofBis[cyclopentadienyl]bis[6-chloro-2-i-butylthio-4-(3-methylbut-1-oxy)pyrimidinyl]titanium

The compound of Example 69 is prepared analogously to the compound ofExample 58, with 6-chloro-2,4-di(3-methylbut-1-oxy)pyrimidine beingreplaced by 6-chloro-2-i-butylthio-4-(3-methylbut-1-oxy)pyrimidine. Thetitle compound is obtained with a melting range of 123°-132° C.

EXAMPLE 70 Preparation of Bis[cyclopentadienyl]bis[2,4-bis(1,1-dimethylpropoxy)pyrimidinyl]titanium

The compound of Example 70 is prepared analogously to the compound ofExample 58, with 6-chloro-2,4-di(3-methylbut-1-oxy)pyrimidine beingreplaced by 5-bromo-2,4-bis(1,1-dimethylpropoxy)pyrimidine. The compoundobtained has a melting range of 135°-145° C.

EXAMPLES 71-78

The preparation of the compounds of Examples 71-78 is carried outanalogously to that of the compound of Example 58, with the startingmaterial used in each case being the 5-brominated pyrimidine derivative.The compounds of Examples 71-78 and their physical data are shown inTable 9.

                  TABLE 9                                                         ______________________________________                                         ##STR46##                                                                                   Melting   Yield Elemental analysis [%]                         Ex.  R         range [°C.]                                                                      [%]   Atom/calculated/found                          ______________________________________                                        71   methyl    118-119   99.8  C:    55.8 55.7                                                               H:    5.5  5.6                                                                N:    10.9 11.0                                72   ethyl     148-165   26.7  C:    60.0 59.8                                                               H:    6.7  6.8                                                                N:    9.3  9.2                                 73   i-propyl  135-145   44.2  C:    63.2 62.2                                                               H:    7.7  7.6                                                                N:    8.2  8.1                                 74   methoxy-  liquid    39.9  C:    55.4 55.6                                     ethyl                     H:    6.7  7.2                                                                N:    7.2  6.8                                 75   3-methyl- liquid    46.3  C:    67.6 68.7                                     but-1-yl                  H:    9.0  9.4                                                                N:    6.6  5.9                                 76   cyclo-    75-85     13.5  C:    70.1 70.3                                     hexyl                     H:    8.3  8.9                                                                N:    6.1  5.4                                 77   cyclo-    127-138   42.9  C:    71.4 70.5                                     hexyl-                    H:    8.8  8.9                                      methyl                    N:    5.6  5.2                                 78   tetra-    wax       36.0  C:    61.5 60.7                                     hydro-                    H:    6.9  6.9                                      furfuryl                  N:    6.0  5.7                                 ______________________________________                                    

EXAMPLE 79 Preparation ofBiscyclopentadienylbis[6-chloro-4-(3-methylbut-1-oxy)-2-phenylpyrimidinyl]titanium

The reaction is carried out under an argon protective-gas atmosphere.8.6 ml of a 1.6M n-butyllithium solution in hexane (13.8 mmol) are addeddropwise to a solution, cooled to 0° C., of 1.95 ml (13.8 ml) ofdiisopropylamine in 12.5 ml of THF. The resultant solution is cooled to-78° C., and a solution of 3.7 g of4-chloro-6-(3-methylbut-1-oxy)-2-phenylpyrimidine in 12.5 ml of THF isadded dropwise. When the mixture has been stirred at -78° C. for 2hours, 1.1 g of solid biscyclopentadienyltitanium dichloride are added.The red suspension is stirred at -78° C. overnight, and excess carbondioxide (solid) is added. The orange-brown solution is then poured into90 ml of water and extracted with ethyl acetate. The organic phases aredried using MgSO₄, filtered and evaporated, giving 4.9 g of a redproduct. Purification on SiO₂ (ethyl acetate: special boiling pointspirit [80°-110° C.] 1:9) gives 0.45 g of starting material, 0.3 g of anorange-red conformational isomer of the product, having a melting rangeof 66°-76° C., and 2.65 g of a yellow conformational isomer of theproduct, having a melting range of 169°-174° C.

Elemental analysis of the orange-red product:

    ______________________________________                                        calc:  C:        65.9%   found:    C:  65.6%                                         H:        5.8%              H:   5.9%                                         N:        7.7%              N:   7.2%                                         Cl:       9.7%              Cl: 10.2%                                  ______________________________________                                    

Elemental analysis of the yellow product:

    ______________________________________                                        calc:  C:        65.9%   found:    C:  63.8%                                         H:        5.8%              H:  5.6%                                          N:        7.7%              N:  7.0%                                          Cl:       9.7%              Cl: 9.0%                                   ______________________________________                                    

EXAMPLE 80 Selective Preparation of the Red Conformational Isomer ofBiscyclopentadienylbis[6-chloro-4-(3-methylbut-1-oxy)-2-phenylpyrimidinyl]titanium

A sulfonation flask is filled under an argon protective gas with 18 mlof distilled THF and 8.3 ml of diisopropylamine puriss., and the mixtureis cooled to -78° C. 36.65 ml of a 1.6M solution of n-butyllithium inhexane are then added dropwise. The solution is stirred at 0° C. for 10minutes. In a second reaction flask, 27 ml of absolute THF, 17.0 g of4-chloro-6-(3-methylbut-1-oxy)-2-phenylpyrimidine and 6.95 g ofbiscyclopentadienyltitanium dichloride are brought into suspension bystirring (resultant suspension is red) and cooled to -20°/-15° C. Thesolution of the lithium diisopropylamine (LDA) is transferred into adropping funnel and slowly added dropwise to the suspension. After halfan hour, the cold solution is poured into a mixture of 60 ml of ethanoland 3.7 ml of acetic acid. The mixture is diluted with water andextracted a number of times with ethyl acetate. The combined organicphases are dried using MgSO₄ and filtered, and the solvent is removed ona rotary evaporator. Flash column chromatography (eluent ethylacetate:petroleum ether 20:80) gives 12.1 g, i.e. a yield of 60%, of theproduct having a melting range of 112°-122° C.

Elemental analysis:

    ______________________________________                                        calc:  C:        65.9%   found:    C:  65.7%                                         H:        5.8%              H:  5.7%                                          N:        7.7%              N:  7.6%                                          Cl:       9.7%              Cl: 9.7%                                   ______________________________________                                    

EXAMPLES 81-90

The compounds of Examples 81-90 are prepared analogously to the compoundof Example 79. The compounds and their data are shown in Table 10 below.

                  TABLE 10                                                        ______________________________________                                         ##STR47##                                                                                                      Elemental                                                     Melting   Yield analysis [%]                                Example                                                                              R          range [°C.]                                                                      [%]   Atom/calc./found                            ______________________________________                                        81     methyl     185-200   53    C:   62.3 62.1                                                                H:   4.2  4.5                                                                 N:   9.1  8.6                                                                 Cl:  11.5 11.0                              82     ethyl (A)* 208-218   18    C:   63.3 63.2                                                                H:   4.7  4.6                                                                 N:   8.7  8.3                                                                 Cl:  11.0 11.0                                     ethyl (B)* 215-220   35    C:   63.3 63.0                                                                H:   4.7  4.8                                                                 N:   8.7  8.2                                                                 Cl:  11.0 11.1                              83     i-propyl   105-115   28    C:   64.2 65.2                                                                H:   5.1  5.4                                                                 N:   8.3  7.8                                                                 Cl:  10.5 9.9                               84     i-butyl    103-115   26.4  C:   65.1 65.5                                                                H:   5.5  5.6                                                                 N:   8.0  7.5                                                                 Cl:  10.1 9.8                               85     decyl      78-88     16.2  C:   69.0 68.3                                                                H:   7.2  7.2                                                                 N:   6.4  6.3                                                                 Cl:  8.2  8.5                               86     2-ethyl-   resin     21.8  C:   67.9 67.9                                     hexyl                      H:   6.7  6.9                                                                 N:   6.9  6.6                                                                 Cl:  8.7  8.4                               87     cyclo-     130-140   25    C:   66.9 67.6                                     hexyl                      H:   5.6  6.0                                                                 N:   7.4  7.0                                                                 Cl:  9.4  8.7                               88     cyclo-     188-196   10    C:   67.6 67.4                                     hexyl-                     H:   5.9  6.0                                      methyl (A)*                N:   7.2  7.0                                                                 Cl:  9.1  9.0                                      cyclo-     85-95     15    C:   67.6 66.9                                     hexyl-                     H:   5.9  5.9                                      methyl (B)*                N:   7.2  6.8                                                                 Cl:  9.1  10.0                              89     methoxy-    94-104   42.2  C:   61.3 61.9                                     ethyl                      H:   4.9  5.2                                                                 N:   7.9  7.6                                                                 Cl:  10.1 9.8                               90     phenoxy-   110-120   22.5  C:   66.6 65.0                                     ethyl                      H:   4.6  4.9                                                                 N:   6.8  6.1                                                                 Cl:  8.6  8.1                               ______________________________________                                         *(A) and (B) are two conformational isomers which can be separated by         column chromatography                                                    

EXAMPLES 91-96

The compounds of Examples 91-96 are prepared analogously to the compoundof Example 79. The compounds and their data are shown in Table 11 below.The substances are obtained as resins, with the exception of thecompound of Example 91, which is a viscous liquid.

                  TABLE 11                                                        ______________________________________                                         ##STR48##                                                                                                      Elemental                                                              Yield  analysis [%]                                Example R         R.sub.1  [%]    Atom/calc./found                            ______________________________________                                        91      3-methyl- n-propyl 40.6   C:   61.7 61.7                                      but-1-yl                  H:   7.0  7.1                                                                 N:   8.5  8.4                                                                 Cl:  10.7 10.0                              92      2-ethyl-  n-propyl 45     C:   64.4 64.9                                      hexyl                     H:   7.8  8.3                                                                 N:   7.5  6.9                                                                 Cl:  9.5  8.5                               93      3-methyl- i-propyl 6.2    C:   61.7 59.8                                      but-1-yl                  H:   7.0  6.6                                                                 N:   8.5  7.8                                                                 Cl:  10.7 10.0                              94      2-ethyl-  i-propyl 41.3   C:   64.4 62.1                                      hexyl                     H:   7.8  7.7                                                                 N:   7.5  7.0                                                                 Cl:  9.5  8.9                               95      3-methyl- decyl    22     C:   67.2 65.3                                      but-1-yl                  H:   8.7  8.9                                                                 N:   6.5  5.9                                                                 Cl:  8.3  6.7                               96      2-ethyl-  decyl    --     C:   68.8 68.5                                      hexyl                     H:   9.2  10.0                                                                N:   6.0  4.8                                                                 Cl:  7.5  5.9                               ______________________________________                                    

EXAMPLES 97 and 98

The compounds of Examples 97 and 98 are prepared analogously to thecompound of Example 79. The compounds and their data are shown in Table12 below.

                  TABLE 12                                                        ______________________________________                                         ##STR49##                                                                                                      Elemental                                                     Melting   Yield analysis [%]                                Example                                                                              R          range [°C.]                                                                      [%]   Atom/calc./found                            ______________________________________                                        97     2-ethylhexyl                                                                             83-95     42    C:   62.6 62.8                                                                H:   5.9  6.1                                                                 N:   6.4  5.9                                                                 Cl:  16.1 15.7                              98     phenoxyethyl                                                                             107-117   15.5  C:   61.5 62.1                                                                H:   4.0  4.3                                                                 N:   6.2  6.1                                                                 Cl:  15.8 15.4                              ______________________________________                                    

EXAMPLES 99 and 100

The compounds of Examples 99 and 100 are prepared analogously to thecompound of Example 79. The compounds and their data are shown in Table13 below.

                  TABLE 13                                                        ______________________________________                                         ##STR50##                                                                                                      Elemental                                                     Melting   Yield analysis [%]                                Example                                                                              R          range [%] [%]   Atom/calc./found                            ______________________________________                                         99    3-methyl-  90-110    65    C:   66.0 66.0                                     but-1-yl                   H:   6.7  6.9                                                                 N:   6.4  6.3                                                                 Cl:  8.1  8.2                               100    2-ethylhexyl                                                                             resin     28.7  C:   67.7 69.7                                                                H:   7.4  7.9                                                                 N:   5.9  5.5                                                                 Cl:  7.4  7.0                               ______________________________________                                    

EXAMPLES 101-103

The compounds of Examples 101-103 are prepared analogously to thecompound of Example 79. The compounds and their data are shown in Table14 below.

                  TABLE 14                                                        ______________________________________                                         ##STR51##                                                                                                      Elemental                                                     Melting   Yield analysis [%]                                Example                                                                              R          range [°C.]                                                                      [%]   Atom/calc./found                            ______________________________________                                        101    3-methyl-  73-83     7.3   C:   70.8 70.8                                     but-1-yl                   H:   5.7  6.2                                                                 N:   6.4  5.6                                                                 Cl:  8.0  7.3                               102    2-ethylhexyl                                                                             73-85     33.5  C:   72.0 72.1                                                                H:   6.7  6.8                                                                 N:   5.8  5.2                                                                 Cl:  7.3  7.0                               103    phenoxyethyl                                                                             110-120   13    C:   71.0 71.0                                                                H:   4.7  5.1                                                                 N:   5.7  5.6                                                                 Cl:  7.2  7.0                               ______________________________________                                    

EXAMPLES 104-110

The compounds of Examples 104-110 are prepared analogously to thecompound of Example 79. The compounds and their data are shown in Table15 below.

                  TABLE 15                                                        ______________________________________                                         ##STR52##                                                                                           Melting      Elemental                                 Ex-                    range  Yield analysis [%]                              ample R        R.sub.1 [°C.]                                                                         [%]   Atom/calc./found                          ______________________________________                                        104   3-methyl-                                                                              octyl   resin  47.0  C:   66.1 65.7                                  but-1-yl                      H:   7.3  7.2                                                                 N:   5.5  5.1                                                                 S:   6.3  6.1                                                                 Cl:  7.0  7.4                             105   ethyl    octyl   resin  15.5  C:   64.3 64.7                                                                H:   6.7  6.9                                                                 N:   6.0  5.5                                                                 S:   6.9  6.3                                                                 Cl:  7.6  7.1                             106   phenoxy- octyl   resin  40.4  C:   66.6 66.8                                  ethyl                         H:   6.3  6.3                                                                 N:   5.0  5.0                                                                 S:   5.7  5.6                                                                 Cl:  6.3  6.2                             107   ethyl    methyl  155-165                                                                              44.6  C:   58.6 59.7                                                                H:   4.6  4.9                                                                 N:   7.6  7.2                                                                 S:   8.7  8.3                                                                 Cl:  9.6  9.1                             108   3-methyl-                                                                              methyl  102-112                                                                              45.0  C:   61.4 61.4                                  but-1-yl                      H:   5.7  5.8                                                                 N:   6.8  6.6                                                                 S:   8.6  8.7                                                                 Cl:  7.8  7.5                             109   2-ethyl- methyl  resin  24.6  C:   63.3 61.4                                  hexyl                         H:   6.5  6.2                                                                 N:   6.2  5.9                                                                 S:   7.8  7.7                                                                 Cl:  7.1  7.0                             110   phenoxy- methyl  101-110                                                                              15.0  C:   62.5 63.3                                  ethyl                         H:   4.6  5.0                                                                 N:   6.1  5.7                                                                 S:   7.0  6.4                                                                 Cl:  7.7  7.2                             ______________________________________                                    

EXAMPLES 111-113

The compounds of Examples 111-113 are prepared analogously to thecompound of Example 79. The compounds and their data are shown in Table16 below.

                  TABLE 16                                                        ______________________________________                                         ##STR53##                                                                                                      Elemental                                   Ex-               Melting   Yield analysis [%]                                ample R           range [°C.]                                                                      [%]   Atom/calc./found                            ______________________________________                                        111   3-methyl-   87-97     20.8  C:   66.0 65.5                                    but-1-yl                    H:   5.3  5.3                                                                 N:   5.9  5.9                                                                 S:   7.5  7.5                                                                 Cl:  6.8  6.7                               112   2-ethylhexyl                                                                              67-77     44.6  C:   67.6 67.9                                                                H:   6.1  6.3                                                                 N:   5.4  5.2                                                                 S:   6.2  6.3                                                                 Cl:  6.9  6.8                               113   phenoxyethyl                                                                               94-104   32.7  C:   66.6 67.7                                                                H:   4.4  4.9                                                                 N:   5.3  5.1                                                                 S:   6.8  6.5                                                                 Cl:  6.1  5.9                               ______________________________________                                    

EXAMPLE 114 Preparation ofBis(cyclopentadienyl)bis[6-chloro-2-(p-N,N-dimethylaminophenyl)-4-(3-methylbut1-oxy)pyrimidinyl]titanium

The preparation of the title compound is carried out analogously to themethod described in Example 79. The compound is obtained in a yield of16% of theory, with a melting range of 105°-115° C.

Elemental analysis:

    ______________________________________                                        calc:  C:        64.8%   found:    C:  64.7%                                         H:         6.4%             H:   6.5%                                         N:        10.3%             N:  10.7%                                         Cl:        8.7%             Cl:  8.8%                                  ______________________________________                                    

EXAMPLE 115 Preparation ofBis(cyclopentadienyl)bis[6-chloro-4-(3-methylbut-1-oxy)-2-pyrrolopyrimidinyI]titanium

The preparation of the tide compound is carried out analogously to themethod described in Example 79. The compound is obtained in a yield of38% of theory, with a melting range of 152°-158° C.

Elemental analysis:

    ______________________________________                                        calc:  C:        61.6%   found:    C:  59.2%                                         H:         5.7%             H:   6.5%                                         N:        11.9%             N:  11.0%                                         Cl:       10.0%             Cl:  9.4%                                  ______________________________________                                    

EXAMPLE 116 Preparation ofBis(cyclopentadienyl)bis[4,6-di(3-methylbut-1-oxy)-2-phenylpyrimidinyl]titanium

The preparation of the title compound is carried out analogously to themethod described in Example 79. The compound is obtained in a yield of37% of theory, with a melting range of 173°-175° C.

Elemental analysis:

    ______________________________________                                        calc:  C:        72.1%   found:    C:  72.3%                                         H:        7.7%              H:  7.8%                                          N:        6.7%              N:  6.6%                                   ______________________________________                                    

EXAMPLE 117 Preparation ofBis(cyclopentadienyl)bis[6-chloro-4-(2-ethylhexyloxy)pyrimidinyl]titanium

The preparation of the title compound is carried out analogously to themethod described in Example 79. The compound is obtained as a resin in ayield of 49% of theory.

Elemental analysis:

    ______________________________________                                        calc:  C:        61.7%   found:    C:  61.9%                                         H:         7.0%             H:   7.4%                                         N:         8.5%             N:   8.1%                                         Cl:       10.7%             Cl: 10.0%                                  ______________________________________                                    

EXAMPLE 118 Preparation ofbis(cyclopentadienyl)-[4-chloro-6-(3-methylbut-1-oxy)-2-phenylpyrimidinyl]acetoxytitanium

69 ml (0.11 mol, 1.6M) of butyllithium are added dropwise over thecourse of 15 minutes under a nitrogen atmosphere to a solution of 15.6ml (0.11 mol) of diisopropylamine in 200 ml of tetrahydrofuran at 0° C.This solution is added dropwise at from -70° to -60° C. over the courseof 2 hours to a suspension of 24.9 g (0.1 mol) of titanocene dichlorideand 27.7 g (0.1 mol) of4-chloro-6-(3-methylbut-1-oxy)-2-phenylpyrimidine in 1000 ml oftetrahydrofuran. The reaction mixture is stirred at -70° C. for 1 hour,allowed to warm to room temperature over the course of about 3 hours andthen poured, with stirring, into water and 19.0 g (0.23 mol) of aceticacid. The resultant red-orange emulsion is filtered through ®Hyflo. Theorganic phase is separated off, dried using magnesium sulfate, filteredand evaporated on a rotary evaporator. The residue is purified by flashchromatography with hexane:ethyl acetate in the ratio 3:1 as eluent,giving 11.2 g (22.4% of theory) of the title compound as a yellow powderhaving a melting point of 158° C.

Elemental analysis:

    ______________________________________                                        calc:  C:        62.4%   found:    C:  62.9%                                         H:        5.8%              H:  5.8%                                          N:        5.6%              N:  4.6%                                          Cl:       7.1%              Cl: 7.0%                                   ______________________________________                                    

EXAMPLE 119 Preparation ofbis(cyclopentadienyl)-[4-chloro-6-(3-methylbut-1-oxy)-2-phenylpyrimidinyl]benzoyloxytitanium

The title compound is prepared analogously to the compound of Example118, with the acetic acid being replaced by benzoic acid. 2.6 g (4.6% oftheory) of the title compound are obtained as an orange powder having amelting point of 118°-120° C.

Elemental analysis:

    ______________________________________                                        calc:  C:        66.1%   found:    C:  66.3%                                         H:        5.6%              H:  5.6%                                          N:        5.0%              N:  4.6%                                          Cl:       6.3%              Cl: 6.4%                                   ______________________________________                                    

EXAMPLE 120 Preparation ofbis(cyclopentadienyl)bis[3,5-dichloro-1-phenylpyrazol-4-yl]titanium

120.1: N-Phenyl-3,5-dichloropyrazole

The preparation of N-phenyl-3,5-dichloropyrazole is carried out by themethod described by A. Michaelis and H. Rohmer in Berichte XXXIII, 3009(1898). However, N-phenyl-3,5-dichloropyrazole is not obtained as asolid having a melting range of 22°-26° C., as described therein, but isobtained as a pale yellow oil.

Elemental analysis of N-phenyl-3,5-dichloropyrazole:

    ______________________________________                                        calc:  C:        50.8%   found:    C:  50.8%                                         H:         2.8%             H:   3.0%                                         N:        13.2%             N:  13.3%                                         Cl:       33.3%             Cl: 32.9%                                  ______________________________________                                    

120.2:

Bis(cyclopentadienyl)[4-chloro-6-(3-methylbut-1-oxy)-2-phenylpyrimidinyl]benzoyloxytitanium

The title product is prepared analogously to the compound of Example 80.However, the 4-chloro-6-(3-methylbut-1-oxy)-2-phenylpyrimidine isreplaced by N-phenyl-3,5-dichloropyrazole. The compound is also isolatedby a different method: after the lithium diisopropylamine has beenadded, the reaction mixture is poured into water/acetic acid, giving ared precipitate. The precipitate is filtered, washed with water anddried, giving 80.4% of theory of the title compound having a meltingrange of 234°-244° C.

Elemental analysis:

    ______________________________________                                        calc:  C:        55.9%   found:    C:  55.9%                                         H:         3.4%             H:   3.8%                                         N:         9.3%             N:   8.9%                                         Cl:       23.6%             Cl: 22.0%                                  ______________________________________                                    

EXAMPLE 121 Reactivity Test in a Varnish

The following components are mixed to give a photocurable composition:

10.0 g of dipentaerythritol monohydroxypentaacrylate, ®SR 399, SartomerCo., Berkshire, GB

15.0 g of tripropylene glycol diacrylate, Sartomer Co., Berkshire, GB

15.0 g of N-vinylpyrrolidone, Fluka

10.0 g of trismethylolpropane triacrylate, Degussa

50.0 g urethane acrylate ®Acrilan AJ20, Societe National des Poudres etExplosifs

0.3 g of flow assistant ®Byk 300, Byk-Mallinckrodt.

Portions of this composition are mixed with 0.3%, based on the solidscontent, of the titanocene photoinitiator according to the invention.All operations are carried out under a red light. The samples mixed withinitiator are applied to a 200 μm aluminium foil. The dry layerthickness is 60 μm. A 76 μm thick polyester film is applied to thislayer, and a standardised test negative having 21 steps of differentoptical density (Stauffer wedge) is laid thereon. The sample is coveredby a second UV-transparent film and pressed against a metal plate bymeans of vacuum. The exposure is carried out in a first test series for5 seconds, in a second test series for 10 seconds and in a third testseries for 20 seconds at a distance of 30 cm by means of a 5 kW lamp.After the exposure, the film and the mask are removed, and the exposedlayer is developed for 10 seconds in ethanol in an ultrasound bath at23° C. The drying is carried out at 40° C. for 5 minutes in afan-assisted oven. The sensitivity of the initiator system used ischaracterised by the indication of the final wedge step imagedtack-free. The higher the number of steps, the more sensitive the testedsystem.

The results are shown in Tables 17 and 18.

                  TABLE 17                                                        ______________________________________                                        Compound    Number of imaged steps                                            from Ex.    after 5s                                                                              10s       20s exposure                                    ______________________________________                                        60          9       12        15                                              61          8       11        13                                              62          8       11        13                                              65          7       10        13                                              72          7        7        11                                              74          8       11        13                                              75          9       11        14                                              ______________________________________                                    

                  TABLE 18                                                        ______________________________________                                        Compound    Number of imaged steps                                            from Ex.    after 5s                                                                              10s       20s exposure                                    ______________________________________                                        58          8       10        13                                              63          7        9        12                                              68          7        9        12                                              73          9       11        15                                              76          7        9        12                                              ______________________________________                                    

EXAMPLE 122 Reactivity Test in a Solder Resist

A composition is prepared from:

37.64 g of pentaerythritol triacrylate ®SR 444, Sartomer Co., Berkshire,GB

10.76 g of hexamethoxymethylmelamine ®Cymel 301, American Cyanamid Corp.

47.30 g of thermoplastic acrylate containing carboxyl groups ®Carboset525,

B.F. Goodrich, Ohio, USA

4.30 g of polyvinylpyrrolidone PVP 30, GAF AG, Zug, Switzerland.

To 100 g of this composition are added

0.5 g of Irgalith Green

319.0 g of methylene chloride and

30.0 g of methanol.

Portions of this composition are mixed with 0.3%, based on the solidscontent, of the titanocene compound to be tested. All operations arecarried out under red light. The samples mixed with initiator areapplied in a dry layer thickness of 30 μm to a 200 μm aluminium foil.The solvent is removed by warming at 60° C. for 15 minutes in afan-assisted oven. A 76 μm thick polyester film is applied to the layer,and a standardised test negative having 21 steps of different opticaldensity (Stauffer wedge) is placed thereon. The sample is covered by asecond UV-transparent film and pressed against a metal plate by means ofvacuum. The sample is then exposed by means of a 5 kW lamp in a firsttest series for 10 seconds, in a second test series for 20 seconds andin a third test series for 40 seconds at a distance of 30 cm. After theexposure, the films and the mask are removed, and the exposed layer isdeveloped with developer A* for 4 minutes at 23° C. in an ultrasoundbath and subsequently dried. The sensitivity of the initiator systemused is characterised by the indication of the final wedge step imagedtack-free. The higher the number of steps, the more sensitive thesystem.

15.00 g of sodium metasilicate.9 H₂ O

0.16 g of potassium hydroxide

3.00 g of polyethylene glycol 6000

0.50 g of levulinic acid

1000.0 g of demineralised water

The results are shown in Tables 19 and 20.

                  TABLE 19                                                        ______________________________________                                        Compound    Number of imaged steps                                            from Ex.    after 10s                                                                              20s      40s exposure                                    ______________________________________                                        61          8        11       13                                              62          8        10       13                                              65          7         9       12                                              ______________________________________                                    

                  TABLE 20                                                        ______________________________________                                        Compound    Number of imaged steps                                            from Ex.    after 10s                                                                              20s      40s exposure                                    ______________________________________                                        58          9        12       15                                              60          9        12       15                                              63          8        10       13                                              64          8        10       13                                              68          8        10       13                                              ______________________________________                                    

EXAMPLE 123 Reactivity in an Etch Resist Formulation

The following components are mixed with a photocurable composition:

10.0 g of dipentaerythritol monohydroxypentaacrylate, ®SR 399, SartomerCo., Berkshire, GB

15.0 g of tripropylene glycol diacrylate, Sartomer Co., Berkshire, GB

15.0 g of N-vinylpyrrolidone, Fluka

10.0 g of trimethylolpropane triacrylate, Degussa

50.0 g urethane acrylate ®Actilan AJ20, Societe National des Poudres etExplosifs

0.3 g of flow assistant ®Byk 300, Byk-Mallinckrodt.

Portions of this composition are mixed with 0.3%, based on the solidscontent, of the titanocene photoinitiator according to the invention.All operations are carried out under a red light. The samples mixed withinitiator are applied in a thickness of 100 μm to a 300 μm aluminiumfoil. The dry layer thickness is 60 μm-70 μm. A 76 μm thick polyesterfilm is applied to this layer, and a standardised test negative having21 steps of different optical density (Stauffer wedge) is laid thereon.The sample is covered by a second UV-transparent polyester film andpressed against a metal plate by means of vacuum. The exposure iscarried out in a first test series for 5 seconds, in a second testseries for 10 seconds and in a third test series for 20 seconds at adistance of 30 cm by means of a 5 kW lamp. After the exposure, the filmand the mask are removed, and the exposed layer is developed for 10seconds in ethanol in an ultrasound bath at 23° C. The drying is carriedout at 40° C. for 5 minutes in a fan-assisted oven. The sensitivity ofthe initiator system used is characterised by the indication of thefinal wedge step imaged tack-free. The higher the number of steps, themore sensitive the tested system. The results are shown in Table 21.

                  TABLE 21                                                        ______________________________________                                        Compound    Number of imaged steps                                            from Ex.    after 5s                                                                              10s       20s exposure                                    ______________________________________                                        107         11      14        17                                              108         12      15        18                                              110         11      13        16                                              111         10      12        15                                              112         11      13        16                                              113         11      13        16                                              114         13      15        18                                              120          9      11        13                                               81         11      14        17                                               82B         8      11        13                                               83          9      12        14                                               84         10      13        15                                               85         11      14        16                                               87         10      12        15                                               88A        10      12        15                                               89         11      14        17                                               90         11      13        16                                               97         11      13        16                                               98         10      12        15                                              101         10      12        15                                              102         12      15        18                                              103         10      13        16                                               99         10      13        16                                              100         10      13        16                                              105         10      12        15                                              106         10      13        16                                              ______________________________________                                    

EXAMPLE 124 Reactivity in a Solder Resist Formulation

A composition is prepared from:

37.64 g of trimethylolpropane triacrylate, Degussa

10.76 g of hexamethoxymethylmelamine ®Cymel 301, American Cyanamid Corp.

47.30 g of polyacrylate containing 3-5% of carboxyl groups ®Carboset525,

B.F. Goodrich, Ohio, USA

4.30 g of polyvinylpyrrolidone PVP 30, GAF AG, Zug, Switzerland.

To 100 g of this composition are added

0.5 g of Irgalith Green

319.0 g of methylene chloride and

30.0 g of methanol.

Portions of this composition are mixed with 0.3%, based on the solidscontent, of the titanocene compound to be tested. All operations arecarried out under a red light. The samples mixed with initiator areapplied in a thickness of 200 μm to a 300 μm aluminium foil. The drylayer thickness is 30-35 μm. The sample is allowed to dry at roomtemperature for 5 minutes. The solvent is then removed by warming at 60°C. for 15 minutes in a fan-assisted oven. A 76 μm thick polyester filmis applied to the layer, and a standardised test negative having 21steps of different optical density (Stauffer wedge) is placed thereon.The sample is covered by a second UV-transparent polyester film andpressed against a metal plate by means of vacuum. The sample is thenexposed by means of a 5 kW lamp in a first test series for 10 seconds,in a second test series for 20 seconds and in a third test series for 40seconds at a distance of 30 cm. After the exposure, the films and themask are removed, and the exposed layer is developed with developer* for4 minutes at 23° C. in an ultrasound bath and subsequently dried for 5minutes at 40° C. The sensitivity of the initiator system used ischaracterised by the indication of the final wedge step imagedtack-free. The higher the number of steps, the more sensitive thesystem.

15.00 g of sodium metasilicate.9 H₂ O

0.16 g of potassium hydroxide

3.00 g of polyethylene glycol 6000

0.50 g of levulinic acid

1000.5 g of demineralised water

The results are shown in Table 22.

                  TABLE 22                                                        ______________________________________                                        Compound    Number of imaged steps                                            from Ex.    after 10s                                                                              20s      40s exposure                                    ______________________________________                                         81         12       14       17                                               82B        12       14       17                                               83         11       14       16                                               84         11       13       16                                               85         11       13       16                                               87         10       12       15                                               88A        10       12       15                                               89         12       14       17                                               90         11       13       16                                               97         12       14       16                                               98         10       12       15                                              101         10       12       15                                              102         13       15       17                                              103         10       12       15                                               99         11       13       16                                              100         11       13       15                                              105         11       13       16                                              106         11       13       16                                              107         12       14       17                                              108         13       16       19                                              110         11       13       16                                              111         11       13       15                                              112         11       13       16                                              113         10       12       15                                              114         15       17       20                                              120         10       12       15                                              ______________________________________                                    

What is claimed is:
 1. A compound of the formula I or II ##STR54## inwhich both R₁ radicals are, independently of one another,cyclopentadienyl.sup.⊖, indenyl.sup.⊖ or4,5,6,7-tetrahydroindenyl.sup.⊖, these radicals being unsubstituted orsubstituted by C₁ -C₁₈ alkyl, C₁ -C₁₈ alkoxy, C₂ -C₁₈ alkenyl, C₅ -C₈cycloalkyl, C₁ -C₄ alkyl-C₅ -C₈ cycloalkyl, phenyl, naphthyl,phenyl-substituted C₁ -C₁₂ alkyl, --Si(R₂)₃, --Ge(R₂)₃, cyano, Cl, Br orI, andthe two R₂ radicals, independently of one another, are C₁ -C₁₂alkyl, C₅ -C₈ cycloalkyl, or unsubstituted or C₁ -C₆ alkyl-substitutedphenyl or benzyl, ##STR55## Q is a radical, Z is --NR₁₀ --, --O-- or--S--, Y is Cl, Br, I, CN, SCN, --O--CO--CH₃, --O--CO--phenyl or--O--SO₂ --CH₃, n is 1 or 2, m is 0 or 1, where the sum of n and m mustbe 2, R₃, R₄ and R₅, independently of one another, are hydrogen, Cl, Br,I, unsubstituted or C₁ -C₄ alkoxy-, C₅ -C₆ cycloalkyl- orphenyl-substituted C₁ -C₁₂ alkyl, unsubstituted or C₁ -C₄alkyl-substituted C₃ -C₈ cycloalkyl or adamantyl, or R₃, R₄ and R₅ arephenyl, pyrryl, furyl, thienyl, imidazolyl, pyridyl, naphthyl, anthryl,phenanthryl or biphenylyl where the radicals phenyl, pyrryl, furyl,thienyl, imidazolyl, pyridyl, naphthyl, anthryl, phenanthryl orbiphenylyl are unsubstituted or substituted by C₁ -C₁₂ alkyl,cyclopentyl, cyclohexyl, Cl, Br, I, C₁ -C₈ alkylthio, --NR₈ R₉, phenyl,phenylthio or/and C₁ -C₁₀ alkoxy, or R₃, R₄ and R₅ are unsubstituted C₂-C₁₂ alkenyl or C₂ -C₁₂ alkenyl which is substituted by unsubstituted orC₁ -C₄ alkyl-, C₁ -C₄ alkoxy-, C₁ -C₄ alkylthio-, Cl-, Br- orI-substituted phenyl or ##STR56## or R₃, R₄ and R₅ are unsubstituted orC₅ -C₈ cycloalkyl- or phenoxy-substituted C₁ -C₁₂ alkoxy, C₂ -C₁₂ alkoxywhich is interrupted by one or more oxygen atoms, unsubstituted or C₁-C₄ alkyl-substituted C₃ -C₁₂ cycloalkoxy, unsubstituted or C₁ -C₄alkoxy- and/or C₁ -C₄ alkyl-substituted phenoxy, unsubstituted or C₁ -C₄alkyl-substituted benzyloxy, tetrahydrofurfuryloxy, C₂ -C₆ alkenyloxy,--O--Si--(R₇)₃, C₁ -C₈ alkylthio, C₃ -C₈ cycloalkylthio, unsubstitutedor C₁ -C₄ alkyl- and/or C₁ -C₄ alkoxy-substituted benzylthio,unsubstituted or C₁ -C₄ alkyl- and/or C₁ -C₄ alkoxy-substitutedphenylthio, --S(O)R₈, --SO₂ R₈, --N(R₉)₂, ##STR57## where R₃ and R₄ arenot simultaneously hydrogen, and at least one radical R₃ or R₄ in the##STR58## radical is unsubstituted or C₅ -C₈ cycloalkyl- orphenoxy-substituted C₁ -C₁₂ alkoxy, C₂ -C₁₂ alkoxy which is interruptedby one or more oxygen atoms, unsubstituted or C₁ -C₄ alkyl-substitutedC₃ -C₁₂ cycloalkoxy, unsubstituted or C₁ -C₄ alkoxy-and/or C₁ -C₄alkyl-substituted phenoxy, unsubstituted or C₁ -C₄ alkyl-substitutedbenzyloxy, tetrahydrofurfuryloxy or C₂ -C₆ alkenyloxy, and in the casewhere Z is --NR₁₀ --, R₃ and R₄ are Cl, Br or I, the two R₆ radicals,independently of one another, are C₁ -C₄ alkyl or C₂ -C₁₀ alkenyl, orthe two R₆ radicals, together with the nitrogen atom to which they arebonded, form a morpholino radical, R₇ is C₁ -C₁₂ alkyl, C₅ -C₈cycloalkyl or unsubstituted or C₁ -C₆ alkyl-substituted phenyl, R₈ isunsubstituted or C₁ -C₄ alkyl-substituted phenyl or α-tertiary C₄ -C₆alkyl, R₉ is unsubstituted or phenyl-, C₇ -C₁₂ alkylphenyl-, C₅ -C₈cycloalkyl- or C₁ -C₄ alkyl-C₅ -C₈ cycloalkyl-substituted C₁ -C₈ alkyl,C₂ -C₈ alkenyl, unsubstituted or C₁ -C₄ alkyl-substituted C₅ -C₈cycloalkyl, C₆ -C₂₀ cycloalkenylalkyl, unsubstituted or C₁ -C₁₂alkyl-substituted phenyl, ##STR59## radical, where, in addition, the twoR₉ radicals in --N(R₉)₂ are identical or different and, together withthe nitrogen atom to which they are bonded, may form a 5- or 6-memberedheterocyclic ring which, in addition to the nitrogen atom, may alsocontain further nitrogen, oxygen or sulfur atoms, or the two R₉radicals, together with the nitrogen atom to which they are bonded, forma ##STR60## radical, R₁₀ is as defined for R₉ or additionally isnaphthyl, biphenylyl, pyridyl or pyrimidinyl, these radicals beingunsubstituted or substituted by Cl, Br, I, NO₂, C₁ -C₁₂ alkyl, C₁ -C₁₀alkoxy, C₁ -C₈ alkylthio, phenylthio, morpholino or --N(C₁ -C₄ alkyl)₂,or R₁₀ is phenyl which is substituted by Cl, Br, I, NO₂, C₁ -C₁₀ alkoxy,C₁ -C₈ alkylthio, phenylthio, morpholino or --N(C₁ -C₄ alkyl)₂, X is--O--, --S--, ##STR61## methylene or ethylene, and A is C₁ -C₁₂ alkyleneor --X--A--X-- is a direct bond.
 2. A compound according to claim 1, inwhich the two R₁ radicals, independently of one another, arecyclopentadienyl.sup.⊖ which is unsubstituted or substituted by C₁ -C₁₈alkyl, C₁ -C₁₈ alkoxy, C₂ -C₁₈ alkenyl, --Si(R₂)₃ or Cl, Br,I.
 3. Acompound of the formula I according to claim 1, in which R₃ and R₅ areunsubstituted or C₅ -C₈ cycloalkyl- or phenoxy-substituted C₁ -C₁₂alkoxy, C₂ -C₁₂ alkoxy which is interrupted by one or more oxygen atoms,unsubstituted or C₁ -C₄ alkyl-substituted C₃ -C₁₂ cycloalkoxy,unsubstituted or C₁ -C₄ alkoxy- and/or C₁ -C₄ alkyl-substituted phenoxy,unsubstituted or C₁ -C₄ alkyl-substituted benzyloxy,tetrahydrofurfuryloxy or C₂ -C₆ alkenyloxy.
 4. A compound according toclaim 1, in which R₅ is C₁ -C₈ alkylthio, C₃ -C₈ cycloalkylthio,unsubstituted or C₁ -C₄ alkyl- and/or C₁ -C₄ alkoxy-substitutedbenzylthio, unsubstituted or C₁ -C₄ alkyl- and/or C₁ -C₄alkoxy-substituted phenylthio, --S(O)R₈ or --SO₂ R₈.
 5. A compound ofthe formula I according to claim 1, in which Q is a ##STR62## radical.6. A compound according to claim 5, in which R₅ is phenyl, pyrryl,furyl, thienyl, imidazolyl, pyridyl, naphthyl, anthryl, phenanthryl orbiphenylyl, where the radicals phenyl, pyrryl, furyl, thienyl,imidazolyl, pyridyl, naphthyl, anthryl, phenanthryl and biphenylyl areunsubstituted or substituted by alkyl, C₁ -C₁₂ cyclopentyl, cyclohexyl,Cl, Br, I, C₁ -C₈ alkylthio, --NR₈ R₉, phenyl, phenylthio or C₁ -C₁₀alkoxy.
 7. A compound of the formula I according to claim 1, in whichR₃, R₄ and R₅, independently of one another, are unsubstituted or C₅ -C₈cycloalkyl- or phenoxy-substituted C₁ -C₁₂ alkoxy, C₂ -C₁₂ alkoxy whichis interrupted by one or more oxygen atoms, unsubstituted or C₁ -C₄alkyl-substituted C₃ -C₁₂ cycloalkoxy, unsubstituted or C₁ -C₄ alkoxy-and/or C₁ -C₄ alkyl-substituted phenoxy, unsubstituted or C₁ -C₄alkyl-substituted benzyloxy, tetrahydrofurfuryloxy or C₂ -C₆ alkenyloxy.8. A compound according to claim 1, in which R₄ is Cl, Br or I.
 9. Acompound of the formula I according to claim 1, in which R₃ isunsubstituted or C₅ -C₈ cycloalkyl- or phenoxy-substituted C₁ -C₁₂alkoxy, C₂ -C₁₂ alkoxy which is interrupted by one or more oxygen atoms,unsubstituted or C₁ -C₄ alkyl-substituted C₃ -C₁₂ cycloalkoxy,unsubstituted or C₁ -C₄ alkoxy- and/or C₁ -C₄ alkyl-substituted phenoxy,unsubstituted or C₁ -C₄ alkyl-substituted benzyloxy,tetrahydrofurfuryloxy or C₂ -C₆ alkenyloxy,R₄ is Cl, and R₅ is phenylwhich is unsubstituted or substituted by C₁ -C₁₂ alkyl, Cl, Br, C₁ -C₈alkylthio, --NR₈ R₉, phenyl, phenylthio or C₁ -C₁₀ alkoxy.
 10. Acompound of the formula I according to claim 1, in which R₃ isunsubstituted or C₅ -C₈ cycloalkyl- or phenoxy-substituted C₁ -C₁₂alkoxy, C₂ -C₁₂ alkoxy which is interrupted by one or more oxygen atoms,unsubstituted or C₁ -C₄ alkyl-substituted C₃ -C₁₂ cycloalkoxy,unsubstituted or C₁ -C₄ alkoxy- and/or C₁ -C₄ alkyl-substituted phenoxy,unsubstituted or C₁ -C₄ alkyl-substituted benzyloxy,tetrahydrofurfuryloxy or C₂ -C₆ alkenyloxy,R₄ is Cl, and R₅ is C₁ -C₁₂alkyl, C₃ -C₈ cycloalkyl or adamantyl.
 11. A compound of the formula Iaccording to claim 1, in which n=2 and m=0.
 12. A compound according toclaim 1, in which Y is Cl, Br or I.
 13. A compound of the formula Iaccording to claim 1, in which Y is Cl, --O--CO--CH₃ or--O--CO--phenyl,R₃ is unsubstituted or C₅ -C₈ cycloalkyl- orphenoxy-substituted C₁ -C₁₂ alkoxy, C₂ -C₁₂ alkoxy which is interruptedby one or more oxygen atoms, C₅ -C₈ cycloalkoxy, benzyloxy,tetrahydrofurfuryloxy or Cl, R₄ is as defined for R₃ or additionallyhydrogen, and R₅ is as defined for R₃ or additionally hydrogen, C₁ -C₁₂alkyl, C₁ -C₈ alkylthio, pyrryl, or phenyl which is unsubstituted orsubstituted by cl, C₁ -C₁₀ alkoxy, phenyl, C₁ -C₈ alkylthio, phenylthioor --NR₈ R₉, and R₁₀ is phenyl.
 14. A compound of the formula Iaccording to claim 1, in which Q is a ##STR63## radical.
 15. A compoundaccording to claim 14, in whichR₃ and R₄ are Cl, Z is --NR₁₀ --, and R₁₀is phenyl which is unsubstituted or substituted by Cl, Br, I, NO₂, C₁-C₁₂ alkyl, C₁ -C₁₀ alkoxy, C₁ -C₈ alkylthio, phenylthio, morpholino or--N(C₁ -C₄ alkyl)₂.
 16. A photopolymerisable composition comprising(a)at least one ethylenically unsaturated, photopolymerisable compound and(b), as photoinitiator, at least one compound of the formula I or II asdefined in claim
 1. 17. A composition according to claim 16, which, inaddition to the photoinitiator (b), also contains at least one furtherphotoinitiator (c) and/or other additives.
 18. A composition accordingto claim 16, containing from 0.05 to 15% by weight of component (b),based on the composition.
 19. A method for the production of paints,printing inks, printing plates, dental compositions, resist materialsand image-recording materials, which comprises incorporating into orapplying to said materials a composition according to claim
 16. 20. Acoated substrate which is coated on at least one surface with acomposition according to claim
 16. 21. A process for the photographicproduction of relief images, wherein a coated substrate according toclaim 20 is exposed imagewise, and the unexposed areas are then removedby means of a solvent.
 22. A process for the photopolymerisation ofnon-volatile, monomeric, oligomeric or polymeric compounds containing atleast one ethylenically unsaturated double bond, wherein a compound ofthe formula I or II according to claim 1 is added to the abovementionedcompounds and the mixture is irradiated with light in the range from 200to 600 nm.
 23. A compound of the formula I ##STR64## in which both R₁radicals are, independently of one another, cyclopentadienyl.sup.⊖, ,indenyl.sup.⊖ or 4,5,6,7-tetrahydroindenyl.sup.⊖, these radicals beingunsubstituted or substituted by C₁ -C₁₈ alkyl, C₁ -C₁₈ alkoxy, C₂ -C₁₈alkenyl, C₅ -C₈ cycloalkyl, C₁ -C₄ alkyl-C₅ -C₈ cycloalkyl, phenyl,naphthyl, phenyl-substituted C₁ -C₁₂ alkyl, --Si(R₂)₃, --Ge(R₂)₃, cyano,Cl, Br or I, andthe two R₂ radicals, independently of one another, areC₁ -C₁₂ alkyl, C₅ -C₈ cycloalkyl, or unsubstituted or C₁ -C₆alkyl-substituted phenyl or benzyl, ##STR65## radical, Z is --NR₁₀ --,--O-- or --S--, Y is Cl, Br, I, CN, SCN or --O--SO₂ --CH₃, n is 1 or 2,m is 0 or 1, where the sum of n and m must be 2, R₃, R₄ and R₅,independently of one another, are hydrogen, Cl, Br, I, unsubstituted orC₁ -C₄ alkoxy- or phenyl-substituted C₁ -C₁₂ alkyl, unsubstituted or C₁-C₄ alkyl-substituted C₃ -C₈ cycloalkyl, unsubstituted or C₁ -C₁₂alkyl-, Cl-, Br-, I-, C₁ -C₈ alkylthio-, --NR₈ R₉ -- or C₁ -C₁₀alkoxy-substituted phenyl, pyrryl, furyl, thienyl, imidazolyl orpyridyl, or R₃, R4 and R₅ are unsubstituted C₂ -C₁₂ alkenyl or C₂ -C₁₂alkenyl which is substituted by unsubstituted or C₁ -C₄ alkyl-, C₁ -C₄alkoxy-, C₁ -C₄ alkylthio, Cl-, Br- or I-substituted phenyl or ##STR66##or R₃, R₄ and R₅ are unsubstituted or C₅ -C₈ cycloalkyl-substituted C₁-C₁₂ alkoxy, C₂ -C₁₂ alkoxy which is interrupted by one or more oxygenatoms, unsubstituted or C₁ -C₄ alkyl-substituted C₃ -C₁₂ cycloalkoxy,unsubstituted or C₁ -C₄ alkoxy- or C₁ -C₄ alkyl-substituted phenoxy,unsubstituted or C₁ -C₄ alkyl-substituted benzyloxy,tetrahydrofurfuryloxy, C₂ -C₆ alkenyloxy, --O--Si--(R₇)₃, C₁ -C₈alkylthio, C₃ ₈ cycloalkylthio, unsubstituted or C₁ -C₄ alkyl- and/or C₁-C₄ alkoxy-substituted benzylthio, unsubstituted or C₁ -C₄ alkyl- and/orC₁ -C₄ alkoxy-substituted thiophenyl, --S(O)R₈, --SO₂ R₈, --N(R₉)₂,##STR67## where R₃ and R4 are not simultaneously hydrogen, and at leastone radical R₃ or R₄ in the ##STR68## radical is unsubstituted or C₅ -C₈cycloalkyl-substituted C₁ -C₁₂ alkoxy, C₂ -C₁₂ alkoxy which isinterrupted by one or more oxygen atoms, unsubstituted or C₁ -C₄alkyl-substituted C₃ -C₁₂ cycloalkoxy, unsubstituted or C₁ -C₄ alkoxy-or C₁ -C₄ alkyl-substituted phenoxy, unsubstituted or C₁ -C₄alkyl-substituted benzyloxy, tetrahydrofurfuryloxy or C₂ -C₆ alkenyloxy,and in the case where Z is --NR₁₀ --, R₃ and R₄ are Cl, Br or I, the twoR₆ radicals, independently of one another, are C₁ -C₄ alkyl or C₂ -C₁₀alkenyl, or the two R₆ radicals, together with the nitrogen atom towhich they are bonded, form a morpholino radical, R₇ is C₁ -C₁₂ alkyl,C₅ -C₈ cycloalkyl or unsubstituted or C₁ -C₆ alkyl-substituted phenyl,R₈ is unsubstituted or C₁ -C₄ alkyl-substituted phenyl or α-tertiary C₄-C₆ alkyl, R₉ is unsubstituted or phenyl-, C₇ -C₁₂ alkylphenyl-, C₅ -C₈cycloalkyl- or C₁ -C₄ alkyl-C₅ -C₈ cycloalkyl-substituted C₁ -C₈ alkyl,C₂ -C₈ alkenyl, unsubstituted or C₁ -C₄ alkyl-substituted C₅ -C₈cycloalkyl, C₆ -C₂₀ cycloalkenylalkyl, unsubstituted or C₁ -C₁₂alkyl-substituted phenyl, a ##STR69## radical, where, in addition, thetwo R₉ radicals in --N(R₉)₂ are identical or different and, togetherwith the nitrogen atom to which they are bonded, may form a 5- or6-membered heterocyclic ring which, in addition to the nitrogen atom,,may also contain further nitrogen, oxygen or sulfur atoms, or, if thetwo R₉ radicals are a ##STR70## group, the two R₉ radicals, togetherwith the nitrogen atom to which they are bonded, form a ##STR71##radical, R₁₀ is as defined for R₉, and if n=2, the formula I alsoincludes compounds of the formula II ##STR72## in which X is --O--,--S--, ##STR73## methylene or ethylene, and A is C₁ -C₁₂ alkylene or--X--A--X-- is a direct bond.